EP2595738B1 - Composition in the form of an emulsion, comprising a hydrophobic phase dispersed in an aqueous phase - Google Patents
Composition in the form of an emulsion, comprising a hydrophobic phase dispersed in an aqueous phase Download PDFInfo
- Publication number
- EP2595738B1 EP2595738B1 EP11754890.9A EP11754890A EP2595738B1 EP 2595738 B1 EP2595738 B1 EP 2595738B1 EP 11754890 A EP11754890 A EP 11754890A EP 2595738 B1 EP2595738 B1 EP 2595738B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- cellulose nanocrystals
- composition
- nanocrystals
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000839 emulsion Substances 0.000 title claims description 106
- 239000000203 mixture Substances 0.000 title claims description 90
- 239000012071 phase Substances 0.000 title claims description 52
- 230000002209 hydrophobic effect Effects 0.000 title claims description 42
- 239000008346 aqueous phase Substances 0.000 title claims description 30
- 229920002678 cellulose Polymers 0.000 claims description 181
- 239000001913 cellulose Substances 0.000 claims description 180
- 239000002159 nanocrystal Substances 0.000 claims description 154
- 238000000034 method Methods 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 16
- 235000019198 oils Nutrition 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 230000000087 stabilizing effect Effects 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000005670 sulfation reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 125000001165 hydrophobic group Chemical group 0.000 claims description 8
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 230000007073 chemical hydrolysis Effects 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 230000001404 mediated effect Effects 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 241000195493 Cryptophyta Species 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 241000894006 Bacteria Species 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 description 155
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 34
- 239000000243 solution Substances 0.000 description 26
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 24
- 229920000742 Cotton Polymers 0.000 description 23
- 229920002749 Bacterial cellulose Polymers 0.000 description 16
- 239000005016 bacterial cellulose Substances 0.000 description 16
- 238000005119 centrifugation Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- 239000000523 sample Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920001610 polycaprolactone Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 230000019635 sulfation Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000007900 aqueous suspension Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- -1 hydroxybutyl Chemical group 0.000 description 5
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 230000021736 acetylation Effects 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 description 4
- 239000008108 microcrystalline cellulose Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005199 ultracentrifugation Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 241000251555 Tunicata Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
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- 150000002334 glycols Chemical class 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
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- 239000011630 iodine Substances 0.000 description 2
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- 229940094522 laponite Drugs 0.000 description 2
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 2
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- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 1
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
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- 239000011019 hematite Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- DBFFAGQMEMIOQB-UHFFFAOYSA-N hexadecane;hydrate Chemical compound O.CCCCCCCCCCCCCCCC DBFFAGQMEMIOQB-UHFFFAOYSA-N 0.000 description 1
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- 238000000265 homogenisation Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
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- 229940038384 octadecane Drugs 0.000 description 1
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- 235000005985 organic acids Nutrition 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001998 small-angle neutron scattering Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/007—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/56—Glucosides; Mucilage; Saponins
Definitions
- the present invention relates to a composition in emulsion form, comprising a hydrophobic phase dispersed in an aqueous phase.
- An emulsion is of the "oil-in-water” type, when (i) the dispersing phase is an aqueous phase and (ii) the dispersed phase is an organic phase (hydrophobic or oily). Such an emulsion is still commonly referred to as "O / W”.
- this physical state of emulsion is not stable: the organic phase tends to cluster to form a single continuous assembly, in particular because of its difference in density with respect to the aqueous phase.
- a first approach consists in using so-called “stabilizing” compounds, conferring on the emulsion rheological properties capable of slowing the phenomenon of coalescence.
- emulsifying compounds are most often emulsifying surfactants (also called “surfactants”) which, thanks to their amphiphilic structure, are placed at the oil / water interfaces and stabilize the dispersed organic droplets.
- surfactants also called “surfactants”
- emulsifying / emulsifying compounds may also consist of solid particles, which make it possible to obtain emulsions known as "Pickering emulsions”.
- Pickering emulsions are emulsions free of surfactants, and which are stabilized by colloidal suspended particles anchored at the oil / water interface.
- microcrystalline cellulose MCC microcrystalline cellulose
- CMC carboxymethyl cellulose
- the document FR-2 794 466 or the document EP-1 057 477 describes the use of cellulose fibrils in cosmetic compositions of the O / W emulsion type, to ensure the stabilization of the latter in the absence of any surfactant.
- the cellulose fibrils employed have a length greater than 1 ⁇ m and preferably ranging from 5 to 40 ⁇ m, for a diameter of between 2 and 100 nanometers. They have a length / diameter ratio equal to or greater than 30.
- the cellulose fibrils used are in a partially amorphous form: they preferably have a degree of crystallinity of less than or equal to 50%, and preferably of between 15% to 50%.
- the object of the invention is to propose new compositions of the oil-in-water emulsion type (advantageously from the family of Pickering emulsions), containing emulsifying particles capable of stabilizing the emulsion, advantageously without a surfactant and that of particularly stable way in time.
- the present invention thus relates to a composition in the form of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase, which composition contains emulsifying particles consisting of elongated cellulose nanocrystals, advantageously still of acicular shape, having a length between 25 nm and 1 ⁇ m, and a width between 5 and 30 nm.
- the cellulose nanocrystals have been the subject of numerous studies, in particular with a view to characterizing their morphology and their crystalline structure.
- such a composition is particularly stable over time, although free of surfactants.
- This emulsion resists in addition to heat treatments, both freeze type heating type.
- the present invention also relates to the use of cellulose nanocrystals as defined above, for stabilizing an emulsion comprising a hydrophobic phase dispersed in an aqueous phase.
- the cellulose nanocrystals provided in step (a) are advantageously obtained by a manufacturing process from a cellulose, said manufacturing process being chosen from one of the following processes: mechanical fractionation, controlled chemical hydrolysis, and dissolution / recrystallization
- the process for producing the cellulose nanocrystals is advantageously followed by a method of post-modification of said cellulose nanocrystals at the end of which their surface charge density and / or their hydrophobicity are modified.
- the post-modification process advantageously consists of a process for introducing or hydrolyzing the groups carrying the surface charges, which groups are preferably chosen from sulphonate, carboxylate and phosphate groups, phosphonate and sulfate.
- the manufacturing process consists of a process for the controlled acid hydrolysis of cellulose with sulfuric acid, to obtain cellulose nanocrystals provided with sulfate groups at the surface; and the optional post-modification process consists of a controlled hydrolysis process of said sulfate groups.
- the manufacturing process consists of a process for the mild acid hydrolysis of cellulose with hydrochloric acid; and the method of Optional post-modification consists of a post-sulfation process of said cellulose nanocrystals.
- the composition according to the invention consists of a composition in the form of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase, and containing emulsifying particles (or in other words "emulsifying particles") consisting of cellulose nanocrystals.
- Emmulsion means a mixture, macroscopically homogeneous but microscopically heterogeneous, of two immiscible liquid phases.
- the emulsion according to the invention is of the type "oil in water", that is to say that (i) the dispersing phase is an aqueous phase and (ii) the dispersed phase is an organic phase (hydrophobic or oily).
- Such an emulsion is still commonly referred to as "O / W”.
- the emulsion according to the invention thus contains cellulose nanocrystals.
- Cellulose nanocrystals are known from the prior art, often under the name of "whiskers” of cellulose or “nanowiskers” of cellulose.
- Such nanocrystals of cellulose can come from various sources: plant (eg wood pulp, cotton or algae), animal (eg tunicate), bacterial, regenerated cellulose or mercerized cellulose. They are for example described in the document Samir et al. (2005, Biomacromolecules, Vol.6: 612-626 ) or in the document Elazzouzi-Hafraoui et al. (Biomacromolecules 2008; 9 (1): 57-65 .).
- cellulose nanocrystals are highly crystalline solid particles.
- cellulose nanocrystals are lacking, or at least substantially free, of amorphous part. They preferably have a degree of crystallinity of at least 60%, and preferably between 60% and 95% (see for example Elazzouzi-Hafraoui et al., 2008 cited above).
- the cellulose nanocrystals have an elongated shape, that is to say advantageously a length / width ratio greater than 1.
- these cellulose nanocrystals have an acicular shape, that is to say a linear and pointed shape reminding a needle.
- This morphology can be observed for example by electron microscopy, in particular by transmission electron microscopy (or "MET").
- these cellulose nanocrystals comprise the following dimensional characteristics: (i) a length of between 25 nm and 1 ⁇ m, and (ii) a width of between 5 and 30 nm.
- length is meant the largest dimension of the nanocrystals, separating two points located at the ends of their respective longitudinal axis.
- width is meant the dimension measured along the nanocrystals, perpendicular to their respective longitudinal axis and corresponding to their maximum section.
- the cellulose nanoparticles form a relatively homogeneous population of nanocrystals whose experimental length values follow a Gaussian distribution centered on the assigned length value for said nanocrystal population.
- cellulose nanocrystals of a "single determined size" can be used, as illustrated in the examples.
- TEM transmission electron microscopy
- AFM atomic force microscopy
- SAXS small-angle neutrons
- SANS Small-Angle Neutron Scattering
- DDL dynamic light scattering
- the cellulose nanocrystals have the following dimensions: (i) a length of between 100 nm and 1 ⁇ m, and (ii) a width of between 5 and 20 nm.
- the cellulose nanocrystals have a length / width ratio greater than 1 and less than 100, preferably between 10 and 55.
- a length / width ratio greater than 1 and less than 100 includes length / width ratios of at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 and 99.
- a length / width ratio of 10 to 55 includes length / width ratios selected from 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53 and 54.
- the nanocrystals obtained from cotton cellulose advantageously have a length of between 100 nm and 200 nm, for a width of between 12 and 15 nm.
- the length / width ratio is advantageously between 7 and 17, and preferably between 10 and 13.
- the nanocrystals can be obtained from a bacterial cellulose.
- Such nanocrystals (known under the name of "bacterial cellulose nanocrystals" or "BCN") advantageously comprise a length of between 600 nm and 1 ⁇ m, for a width of between 12 and 17 nm.
- the length / width ratio is advantageously between 35 and 83, preferably between 45 and 55.
- the cellulose nanocrystals are advantageously chosen according to their surface characteristics, taking into account in particular (i) the electrostatic appearance and / or (ii) hydrophobicity or hydrophilicity .
- the emulsion stabilizing cellulose nanocrystals advantageously have a maximum surface charge density of 0.5 e.nm -2 , and preferably a maximum surface charge density of 0.31 e .nm -2 .
- "e” corresponds to an elementary charge.
- the surface charge density and the ionic strength of the aqueous phase are advantageously adapted relative to one another.
- this surface charge density is determined by conductimetric assay; a particular embodiment is described below in the Examples section.
- the cellulose nanocrystals comprise a charged surface, with a surface charge density of between 0.01 e.nm -2 and 0.31 e.nm -2 .
- the desired density of surface charges can be obtained by controlling the degree of sulfation of the nanocrystals.
- the degree of sulfation of the nanocrystals can be controlled by subjecting the cellulose nanocrystals to a sulfation treatment and, if necessary, subsequent desulfation treatment.
- Applicant has shown that a stable Pickering emulsion is obtained when substantially uncharged cellulose nanocrystals are used.
- the Applicant has also shown that beyond 0.31 e.mm -2 , the stability of the Pickering emulsion is very significantly altered.
- the Applicant has shown that cellulose nanocrystals having an excessively high charge density value have an excessively hydrophilic surface and are found in large amounts in suspension in the aqueous phase instead of being located at the oil / water interface to stabilize the emulsion.
- the cellulose nanocrystals advantageously comprise negative surface charges, which are advantageously carried by anionic groups on the surface.
- the anionic groups of the cellulose nanocrystals are chosen, for example, from sulphonate groups, carboxylate groups, phosphate groups, phosphonate groups and sulphate groups.
- a degree of substitution value (DS) to the corresponding value of surface charge density (e.mm -2 ) is direct, since the number of charges of the considered chemical group is known.
- DS degree of substitution value
- surface charge density e.mm -2
- these cellulose nanocrystals have a degree of substitution (DS) of between 10 -3 and 10 -2 e / nm 2 , or a degree of surface substitution (DSs) of between DS / 0.19 at DS / 0.4, according to the morphology of the nanocrystals used.
- DS degree of substitution
- DSs degree of surface substitution
- the cellulose nanocrystals have a neutral surface.
- the density of surface charges is advantageously less than or equal to 0.01 e.nm -2 .
- the charge density of the cellulose nanocrystals is advantageously chosen as a function of the ionic strength of the aqueous phase of the composition.
- the cellulose nanocrystals used according to the invention advantageously consist of cellulose nanocrystals which have not undergone any hydrophobization treatment.
- the cellulose nanocrystals that are used to obtain the Pickering emulsion do not undergo any subsequent chemical processing, other than a desulfation or sulfation treatment.
- cellulose nanocrystals which have not been functionalized or grafted with groups allowing their subsequent crosslinking, for example by groups of the methacrylate or dimethacrylate type are preferably used.
- cellulose nanocrystals which have not been functionalized or grafted with polymer molecules, such as polyethylene glycol, a poly (hydroxyester) or a polystyrene are preferably used.
- the Applicant has also shown that the stability of the Pickering emulsion can be increased by using an aqueous phase having a determined minimum ionic strength.
- the ionic strength threshold value of the aqueous phase from which optimal stability of the emulsion is obtained is that for which the charges (counter-ions) present in the aqueous phase neutralize the charges (ions) present on the nanocrystals.
- the presence of excess counterions does not significantly affect the stability properties of the emulsion.
- the cellulose nanocrystals advantageously have a maximum surface charge density of 0.03 e.nm -2 .
- the surface charge density carried by the cellulose nanocrystals does not seem to be a relevant parameter for the effective stabilization of the emulsion.
- An ionic strength greater than the ionic strength equivalent to 10 mM NaCl includes an ionic strength greater than 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 275, 280, 290, 300, 310, 315, 320, 325, 330, 335, 340, 345, 350, 360, 370, 375, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or greater than 500 mM NaCl.
- the ionic strength is less than an ionic strength equivalent to 3 M NaCl.
- the stability of said emulsions is already maximal for an ionic strength of the composition of 20 mM NaCl, and the level of stability of the emulsion being kept substantially unchanged for all ionic strength values tested, i.e. at least up to an ionic strength value equivalent to the ionic strength of 0.5 M NaCl.
- the cellulose nanocrystals comprise hydrophobic groups on the surface.
- the density of hydrophobic groups at the surface may be an interesting parameter to take account of the interfacial tension (nature of the aqueous phase and the oily phase).
- Such hydrophobic groups are advantageously chosen from acetyl, alkyl, aryl, phenyl, benzyl, hydroxybutyl, hydroxypropyl and polycaprolactone (or PCL) groups.
- the cellulose nanocrystals are generally incorporated into the aqueous phase of the composition.
- the Pickering emulsion composition is stabilized solely by the cellulose nanocrystals, without the addition of other emulsifying or stabilizing compounds.
- the Pickering emulsion composition does not include any solid, non-functionalized, or functionalized particles other than cellulose nanocrystals.
- composition is stabilized by the cellulose nanocrystals, reported in combination with at least one other compound having emulsifying properties and / or stabilizing properties, for example with or without surfactant (s).
- the Pickering composition of the invention may contain CTAB (hexadecyltrimethylammonium bromide).
- the composition advantageously comprises from 0.035% to 2% by weight, more preferably from 0.05% to 1% by weight, of cellulose nanocrystals relative to the total weight of said composition.
- This mass proportion of cellulose nanocrystals may be evaluated, for example, by dry extract of the aqueous phase or by determination of the sugars after hydrolysis.
- a sufficient amount of cellulose nanocrystals to obtain a coverage ratio of at least 60% is preferred for the preparation of a Pickering emulsion composition.
- a mass of nanoparticles that is too small relative to the volume of oil it is likely to coalesce the droplets of the hydrophobic phase so as to tend towards a minimum coverage of 60%.
- the "recovery rate" by cellulose nanocrystals represents the proportion of the surface of the hydrophobic phase droplets dispersed in the aqueous phase, at the oil / water interface, which is covered by the nanocrystals of cellulose.
- the surface of the nanocrystals is likened to a single-plane surface, assuming that the nanocrystals are aligned on said surface in a flat ribbon.
- the area of the droplets is the area at the oil / water interface, which has been calculated for each average droplet diameter according to D (3,2).
- the hydrophobic dispersed phase advantageously represents less than 50% by volume relative to the total volume of the composition.
- the hydrophobic phase advantageously represents from 5% to 45% by volume relative to the total weight of the composition.
- the hydrophobic phase is selected from vegetable oils, animal oils, mineral oils, synthetic oils, hydrophobic organic solvents and hydrophobic liquid polymers.
- the Pickering emulsion composition according to the invention may also contain any other compound suitable for its use or final destination.
- This Pickering emulsion composition can thus be adapted to the application advantageously chosen from food compositions, cosmetic compositions, pharmaceutical compositions and phytosanitary compositions.
- composition may contain, for example, without being limiting, active principles and adjuvants such as preservatives, gelling agents, solvents, dyestuffs, etc.
- the hydrophobic phase is chosen from vegetable oils, animal oils, mineral oils, synthetic oils, hydrophobic organic solvents and hydrophobic liquid polymers.
- the hydrophobic phase may be selected from a substituted or unsubstituted alkane or cycloalkane.
- an alkane having more than 5 carbon atoms includes alkanes having more than 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or more than 17 carbon atoms. that is to say, according to the conventional nomenclature, C 6 -C 18 alkanes and which are of formula C n H 2n + 2 . Said alkanes may be linear or branched.
- Said alkanes include linear, cyclic or branched alkanes of the hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane types.
- the substituted alkanes include the above straight or branched alkanes of which at least one hydrogen atom is substituted with a halogen selected from chlorine, bromine, iodine or fluorine.
- the substitution of at least one hydrogen atom includes the substitution of 2, 3, 4 or 5 hydrogen atoms.
- said cycloalkane is unsubstituted or substituted cyclohexane.
- the cyclohexane may be substituted with 1, 2, 3 or 4 halogen atoms selected from chlorine, bromine, iodine or fluorine.
- the hydrophobic phase may further comprise a mixture of such alkanes, for example in the form of a paraffin oil.
- the hydrophobic phase comprises one or more polymerizable hydrophobic monomers of a known type.
- the hydrophobic phase consists essentially of a composition of a hydrophobic monomer or a mixture of hydrophobic monomers.
- the hydrophobic phase may consist essentially of a styrene monomer composition.
- hydrophilic phase or "aqueous phase” means an immiscible liquid with the hydrophobic phase.
- a hydrophilic phase which is miscible with water is preferably used.
- the hydrophilic phase may be water, as illustrated in the examples.
- the hydrophilic phase may be a hydrophilic solvent, preferably a solvent carrying hydroxyl groups, such as glycols.
- the glycols include glycerol and polyethylene glycols.
- the hydrophilic phase may also contain water-soluble texturizing agents, in particular thickening or viscosifying agents, such as polysaccharides (for example dextran or xanthan, the latter being widely used in food applications).
- the hydrophilic phase may consist, in part or totally, of an organic liquid selected from an alcohol such as ethanol, or else acetone.
- the hydrophilic phase may comprise a single liquid or a mixture of several liquids.
- the general steps for the manufacture of the emulsion can be carried out according to conventional procedures, especially used for the manufacture of Pickering emulsion.
- a technique for obtaining an ultrasonic emulsion can be used.
- the step of incorporating the cellulose nanocrystals in the aqueous phase corresponds to the steps used for the incorporation of colloidal particles during the manufacture of Pickering emulsions.
- the cellulose nanocrystals provided in step (a) are advantageously obtained by a manufacturing process from a cellulose.
- the cellulose is advantageously chosen from at least one of the following celluloses: vegetable, animal, bacterial, algal or regenerated from a cellulose transformed from commercial sources.
- the main source of cellulose is vegetable fiber.
- Cellulose is present as a component of the cell wall, in the form of bundles of micro-fibrils.
- micro-fibrils Part of these micro-fibrils is composed of so-called “amorphous” cellulose, while a second part consists of "crystalline” cellulose.
- the cellulose nanocrystals are advantageously derived from crystalline cellulose isolated from plant fibers, by elimination of the amorphous cellulose part.
- plant sources are cotton, birch, hemp, ramie, flax, spruce.
- algal sources of cellulose there may be mentioned for example Valonia or Chladophora.
- Gluconoacetobacter xylinus which produces Nata de coco by incubation directly in coconut milk.
- tunicier Among the animal sources of cellulose, there may be mentioned for example the tunicier.
- the cellulose can also be regenerated from a commercially-processed cellulose, especially in the form of paper.
- Whatman (registered trademark) filtration paper can be used to obtain cotton cellulose.
- the cellulose may also consist of a so-called “mercerized” cellulose (mercerization consists of a treatment of cellulose generally based on sodium hydroxide).
- the process for producing the nanocrystals is advantageously chosen from one of the following processes: mechanical fractionation, controlled chemical hydrolysis, and dissolution / recrystallization
- mechanical fractionation is meant a conventional operation of high pressure homogenization.
- controlled chemical hydrolysis is meant treatment with an acidic chemical compound of cellulose, under conditions ensuring the removal of its amorphous part.
- the acidic chemical compound is advantageously chosen from sulfuric acid or hydrochloric acid.
- the surface charge can be modulated.
- hydrolysis with hydrochloric acid will lead to a virtually neutral surface state, while hydrolysis by sulfuric acid will introduce sulphate fillers (SO 3 - group ) to the surface of the cellulose nanocrystals.
- dissolution / recrystallization treatment with a solvent, for example phosphoric acid, urea / NaOH, ionic liquids, etc., followed by recrystallization.
- a solvent for example phosphoric acid, urea / NaOH, ionic liquids, etc.
- the cellulose nanocrystals obtained Prior to their integration into the composition, the cellulose nanocrystals obtained are advantageously subjected to a post-modification process, at the end of which their surface charge density and / or their hydrophobicity / hydrophilicity are modified.
- This post-modification aims to optimize the surface characteristics of the cellulose nanocrystals, in particular according to the emulsion in which they are introduced, in order to optimize its stabilization.
- the post-modification process advantageously consists of a process for introducing or hydrolyzing surface groups carrying said surface charges.
- the post-modification operation comprises a step of introducing or hydrolyzing surface groups chosen from sulphonate, carboxylate, phosphate, phosphonate and sulphate groups.
- the manufacturing process consists of a process for the acidic hydrolysis of the cellulose with sulfuric acid, to obtain cellulose nanocrystals provided with sulfate groups on the surface.
- the post-modification process consists of a controlled hydrolysis process of said sulfate groups, that is, for example by an acid treatment (chosen, for example, from hydrochloric acid or trifluoroacetic acid) for a time adapted to the degree of hydrolysis sought.
- an acid treatment Chosen, for example, from hydrochloric acid or trifluoroacetic acid
- the manufacturing process consists of a process for the controlled acid hydrolysis of cellulose with hydrochloric acid.
- the optional post-modification process consists of a post-sulfation process of said cellulose nanocrystals.
- Such post-sulfation is advantageously carried out by acid treatment of the nanocrystals with sulfuric acid.
- the post-modification process advantageously consists of a process for introducing or hydrolyzing groups having a hydrophobic character.
- hydrophobic groups that can be introduced or removed include alkyl, aryl, phenyl, benzyl, acetyl, hydroxybutyl, hydroxypropyl, polycaprolactone (or PCL).
- the figure 1 illustrates the influence of the ionic strength of the emulsion composition on the stability of said emulsion.
- the ionic strength values expressed in the final molar concentration of NaCl of the aqueous phase.
- the volume fraction of emulsion expressed as a percentage by volume.
- Protocol 1 Preparation of bacterial cellulose nanocrystals
- BCN fragments are nanofibrilated in a Waring blender, at full speed, in an aqueous suspension containing ice cubes so as to combine shear and impact stresses.
- the paste thus obtained is drained through polyamide filters and then suspended in a 0.5 N sodium hydroxide solution with stirring in a closed flask for two hours at 70 ° C.
- a bleaching step is performed with chlorite to obtain a hollocellulose-type compound, as described in Gilkes et al. ( Gilkes, NR; Jervis, E .; Henrissat, B .; Tekant, B .; Miller, RC; Warren, RAJ; Kilburn, DG, The adsorption of a bacterial cellulase and its 2 isolated domains to crystalline cellulose. J. Biol. Chem. 1992, 267 (10), 6743-6749 ).
- a solution of NaClO 2 , 17 g / L is mixed with an identical volume of acetate buffer pH 4.5 (27 g of NaOH + 75 g of acetic acid per liter).
- the bleached bacterial cellulose is then suspended and heated with stirring at 70 ° C for two hours with reflux.
- This bacterial cellulose is then hydrolysed using a hydrochloric acid solution (2.5 N, two hours under reflux).
- the acidic compounds are removed by the successive operations until neutrality: centrifugation (10000 g for 5 minutes) and dispersion in a purified solution 18 Mohm.
- the cellulose nanocrystals thus obtained are stored at 4 ° C. in the form of a 1% suspension, with addition of a drop of CHCl 3 per 250 ml of suspension.
- Protocol 2 Preparation of post-sulfated bacterial cellulose nanocrystals
- the nanocrystals are then deposited by centrifugation (10000 g / 5 min).
- the product obtained is mixed with glass beads (diameter 3 mm) and then centrifuged again (10000 g / 10 min).
- the glass beads coated with sulfated nanocrystals are kept dry for two hours at 40 ° C.
- the beads are then dried in a desiccator in the presence of P 2 O 5 at 50 ° C for 14 hours.
- the sulphated cellulose nanocrystals are recovered by washing the beads with distilled water, and successive centrifugation from 10,000 rpm to 76,000 rpm for 10 to 30 minutes to obtain a colloidal suspension.
- Protocol 3 Desulfation of post-sulfated bacterial cellulose nanocrystals
- the suspension of 2.2% bacterial cellulose nanocrystals, post-sulfated according to protocol 2 is heated for three hours at 100 ° C. in 2.5 N HCl and then washed by centrifugation at 6000 rpm for 5 minutes. six times.
- TMD-8 mixed bed resin The collected product is then dialyzed to neutrality, and residual electrolytes are removed on an ion exchange resin (TMD-8 mixed bed resin).
- 25 g of paper is wetted in 700 ml of deionized water, and the solution is mixed until a homogeneous mixture is obtained. The excess water is then removed by filtration.
- the product obtained is suspended in 500 ml of a 61% sulfuric acid solution, maintained at 72 ° C. with stirring for 30 minutes.
- the suspension is then cooled, washed with ultrapure water by successive centrifugations at 8000 rpm for 15 minutes, and dialyzed until neutral for three days with a reception phase consisting of distilled water.
- the residual electrolytes are then extracted using a mixed-bed resin (TMD-8, hydrogen and hydroxyl form) for 4 days.
- TMD-8 mixed-bed resin
- the final dispersion consisting of sulphated cotton, is stored at 4 ° C.
- Protocol 5 Desulfation of sulfated cotton nanocrystals
- the desulfation of the sulphated cotton nanocrystals according to protocol 4 is carried out by an acid treatment, using 5 ml of a solution of 5 N HCl or a solution of 10 N trifluoroacetic acid (TFA), added to 5 mL of a suspension of sulfated cotton nanocrystals at a concentration of 13 g / L.
- TFA trifluoroacetic acid
- This acid treatment is carried out in a closed container and heated at 98-100 ° C with stirring, for 1, 2, 5 or 10 hours.
- the two products obtained were rinsed with water by centrifugation (six times, 6000 rpm for 5-7 minutes).
- Protocol 6 Measurement of sulfation degree by conductimetric titration
- the conductimetric titration makes it possible to determine the degree of sulfation of the cellulose nanocrystals.
- Protocol 7 Transmission Electron Microscopy (TEM)
- This grid for electron microscopy is then dried in an oven at 40 ° C.
- Protocol 8 Preparation of an O / W Emulsion Stabilized by Nanocrystals
- a first oil-in-water Pickering emulsion is prepared using an aqueous phase containing a known concentration of cellulose nanocrystals.
- the other emulsions were prepared using a 30/70 oil / water ratio from an aqueous phase containing nanoparticles at a concentration of 0.5% by weight, based on the weight of the emulsion (without further dilution) .
- hexadecane is added to 0.7 mL of the aqueous suspension; for 30 seconds, the mixture is subjected to a treatment alternating 2 seconds of ultrasound treatment and 5 seconds of rest.
- Protocol 9 Stability test, optical microscopy
- the emulsions obtained according to protocol 8 are centrifuged for 30 seconds at 10,000 g. Given the difference in density between hexadecane and water, creaming is observed. The emulsion volume is evaluated before and after centrifugation.
- the droplet diameter is measured from the images obtained by image analysis using an "imageJ" program.
- 280-380 mg of a styrene / initiator mixture (ratio st: V-65 120: 1 w / w) are mixed with 1, 0 to 1.5 mL of 0.5% solution of a water sample solution, sonicated for 1-2 min and degassed with nitrogen for 10 minutes.
- the emulsion was ultrasonically obtained for 30 seconds (pulse of 3 seconds, separated by 5 seconds).
- This system is degassed with nitrogen for 10 minutes, and the polymerization took place at 63 ° C without stirring for 24 hours.
- the resulting preparation is subjected to a metallization step according to conventional techniques of scanning electron microscopy, before observation.
- Protocol 11 Acetylation of bacterial cellulose nanocrystals
- the water is gradually replaced by acetic acid by distillation on a rotary evaporator (the temperature of the water bath is below 40 ° C), then centrifuged five times (5 minutes at 10000 g).
- the two parts are mixed and heated at 40 ° C. for 5 minutes and for 1 minute with 6 ⁇ l of a 5% catalyst.
- the sample solution is observed under polarized light so as to detect the presence of liquid crystals.
- the reaction is stopped by the addition of water (ratio 1: 1 v / v), either after one minute for one part (B1), or after three minutes for the other part (B2).
- the resulting product is mixed with a mixed bed resin for three hours and then filtered.
- Protocol 12 Acetylation of cotton cellulose nanocrystals
- the water is gradually replaced by acetic acid by distillation on a rotary evaporator (the temperature of the water bath was below 40 ° C), and then centrifugation 5 times 7min at 10000g.
- the two fractions were heated at 60 ° C with 190 ⁇ l of catalyst, i.e. 5% by weight sulfuric acid solution in acetic acid, and stirred.
- the reaction is stopped after 1.5 min for the first fraction, and after 0.5 min for the second.
- an ultracentrifugation (65,000 rpm for 15-30 min) of the second sample solution obtained is carried out in order to collect and rinse the products; residual electrolytes are removed by ion exchange resin for 3 hours before filtration.
- reaction is stopped after 1 min by the addition of water in the ratio 1: 1 v / v.
- the other part (c-wh 4) is heated at 40 ° C. with stirring for 5 minutes, and then 5 ml of a mixture consisting of 98% acetic anhydride and 100% acetic acid in a ratio are added. 1: 1 v / v.
- the two samples are washed with water by centrifugation, and kept with a bed of resin for 3 hours, then filtered.
- Protocol 13 Surface grafting of poly-caprolactone
- the surface grafting of poly- ⁇ -caprolactone is carried out on BCN and cotton whiskers.
- the solution is heated to 95 ° C; 27 ⁇ l of Sn (Oct) 2 is added under a nitrogen atmosphere.
- the polymerization is continued for 18 h, before redispersion of the product in 2 mL of THF, filtered and rinsed with methanol.
- the nanocrystals of bacterial cellulose are obtained according to protocol 1, and consist of neutral particles.
- these nanocrystals have excellent properties for forming particularly stable Pickering emulsions.
- Such emulsions were made according to protocol 8, for different hexadecane / aqueous phase ratios, namely from a 10:90 ratio to a 50:50 ratio.
- the particle concentration in the emulsions varies with the volume fraction of the water in said emulsions.
- the main difference concerns the rate of aggregation which decreases with the decrease in the amount of particles per mL of hydrophobic phase.
- the bacterial cellulose nanocrystals obtained according to the protocols 1 to 5, are characterized by transmission electron microscopy according to protocol 7.
- the surface characteristics of nanocrystals and the characteristics of the emulsion are determined according to the protocols 6 and 9.
- the results obtained are summarized in the following Table 2. ⁇ u> Table 2 ⁇ / u> Sample Length / thickness in nm DS (sulphate / sugar) Density of charge (sulfate / nm 2 ) No.
- the charge density can be expressed indifferently in e.nm -2 or in sulfate.nm-2, because the sulfate ion carries a single charge.
- the electron microscopic analyzes show that the particles all have an elongated shape.
- the BCN is decreased from 919 nm to 644 nm without significant variation in width after the sulfation step.
- hydrolysis with hydrochloric acid tends to peel the surface of the cellulose nanocrystals and thus reduce or even eliminate the sulfate groups, and thus reduce or eliminate the corresponding charges.
- the corresponding emulsion is very stable (at least one year), and resists freezing and heating (2 hours at 80 ° C).
- Emulsions were prepared from cotton cellulose nanocrystals as described in Protocol 8.
- liquid aqueous media having increasing values of final NaCl concentration were used, as shown in Table 3 below.
- Table 3 ⁇ u> Table 3 ⁇ / u> NaCl (M) Thickness (mm) % volumic Zeta pot (mV) 0 0 0 -55 0.02 9.2 42.6 -35 0.05 9.6 44.4 -25 0.08 9.5 44.0 -10 0.1 9 41.9 ⁇ 0 0.2 9.08 42.0 ND * 0.5 7.97 36.9 ND * ND: Not determined
- Table 3 show the evolution of the thickness of the emulsion obtained after creaming (centrifugation); it is a relative value in mm, an emulsified volume percentage and zeta potential values which illustrates the level of screening of the surface charges by the added NaCl.
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Description
La présente invention concerne une composition sous forme d'émulsion, comprenant une phase hydrophobe dispersée dans une phase aqueuse.The present invention relates to a composition in emulsion form, comprising a hydrophobic phase dispersed in an aqueous phase.
Une émulsion est du genre « huile dans eau », lorsque (i) la phase dispersante est une phase aqueuse et (ii) la phase dispersée est une phase organique (hydrophobe ou huileuse). Une telle émulsion est encore désignée couramment par le sigle « H/E ».An emulsion is of the "oil-in-water" type, when (i) the dispersing phase is an aqueous phase and (ii) the dispersed phase is an organic phase (hydrophobic or oily). Such an emulsion is still commonly referred to as "O / W".
Or, cet état physique d'émulsion n'est pas stable : la phase organique a tendance à se regrouper pour ne former qu'un seul ensemble continu, notamment en raison de sa différence de densité par rapport à la phase aqueuse.However, this physical state of emulsion is not stable: the organic phase tends to cluster to form a single continuous assembly, in particular because of its difference in density with respect to the aqueous phase.
Pour obtenir cette stabilité, une première approche consiste à employer des composés dits « stabilisant », conférant à l'émulsion des propriétés rhéologiques aptes à ralentir le phénomène de coalescence.To obtain this stability, a first approach consists in using so-called "stabilizing" compounds, conferring on the emulsion rheological properties capable of slowing the phenomenon of coalescence.
Pour stabiliser les émulsions, une autre démarche consiste à employer des composés dits « émulsifiant » ou « émulsionnants ».Another approach to stabilize emulsions is to use compounds known as "emulsifiers" or "emulsifiers".
Ces composés émulsifiants sont le plus souvent des agents tensio-actifs émulsionnants (dits encore « agents de surface ») qui, grâce à leur structure amphiphile, se placent à l'interfaces huile/eau et stabilisent les gouttelettes organiques dispersées.These emulsifying compounds are most often emulsifying surfactants (also called "surfactants") which, thanks to their amphiphilic structure, are placed at the oil / water interfaces and stabilize the dispersed organic droplets.
Cependant, les composés émulsifiants de ce genre n'offrent pas toujours la stabilité recherchée dans le temps. De plus, les agents tensio-actifs de synthèse présentent souvent des inconvénients sur le plan écologique.However, emulsifying compounds of this kind do not always offer the desired stability over time. In addition, synthetic surfactants often have ecological disadvantages.
Ces composés émulsifiants/émulsionnants peuvent également consister en des particules solides, qui permettent l'obtention d'émulsions dites « émulsions de Pickering ».These emulsifying / emulsifying compounds may also consist of solid particles, which make it possible to obtain emulsions known as "Pickering emulsions".
Les émulsions de Pickering sont des émulsions dépourvues d'agents tensio-actifs, et qui sont stabilisées par des particules en suspension colloïdales venant s'ancrer à l'interface huile/eau.Pickering emulsions are emulsions free of surfactants, and which are stabilized by colloidal suspended particles anchored at the oil / water interface.
Contrairement aux agents tensio-actifs qui s'adsorbent et se désorbent continuellement, les particules en suspension colloïdale s'adsorbent fortement aux interfaces (voire même de manière irréversible).In contrast to surfactants that continuously adsorb and desorb, particles in colloidal suspension strongly adsorb at interfaces (or even irreversibly).
Ces émulsions de Pickering présentent en pratique des propriétés très originales et intéressantes, notamment en comparaison avec des émulsions classiques stabilisées par des agents tensio-actifs.These Pickering emulsions in practice have very original and interesting properties, especially in comparison with conventional emulsions stabilized by surfactants.
En particulier, il est possible de fabriquer très facilement des émulsions, allant du micromètre au centimètre, en exploitant notamment le phénomène dit de « coalescence limitée ». De plus, les compositions obtenues sont beaucoup plus stables que leurs homologues stabilisées par des agents tensio-actifs.In particular, it is possible to very easily manufacture emulsions, ranging from micrometer to centimeter, exploiting in particular the so-called phenomenon of "limited coalescence". In addition, the compositions obtained are much more stable than their counterparts stabilized with surfactants.
Pour illustrer une telle émulsion de Pickering, le document
Le document
Le document
Mais ce document présente encore des résultats qui montrent une efficacité limitée, voire une inefficacité, de la cellulose microcristalline pour stabiliser les émulsions.But this document still presents results which show a limited efficiency, or even an inefficiency, of the microcrystalline cellulose to stabilize the emulsions.
Par ailleurs, le document
Les fibrilles de cellulose employées ont une longueur supérieure à 1 µm et de préférence allant de 5 à 40 µm, pour un diamètre compris entre 2 et 100 manomètres. Elles présentent un rapport longueur/diamètre égal ou supérieur à 30.The cellulose fibrils employed have a length greater than 1 μm and preferably ranging from 5 to 40 μm, for a diameter of between 2 and 100 nanometers. They have a length / diameter ratio equal to or greater than 30.
De plus, les fibrilles de cellulose utilisées sont sous une forme partiellement amorphe : elles présentent de préférence un taux de cristallinité inférieur ou égal à 50 %, et de préférence compris entre 15 à 50 %.In addition, the cellulose fibrils used are in a partially amorphous form: they preferably have a degree of crystallinity of less than or equal to 50%, and preferably of between 15% to 50%.
Or, il s'avère que de telles fibrilles de cellulose d'une longueur supérieure à 1 µm ne permettent pas l'obtention d'émulsions calibrées de taille contrôlée et homogène, et par conséquent ne permettent pas la faisabilité d'émulsions monodisperses avec des tailles de gouttelettes organiques réduites. En fait, avec ces fibrilles de cellulose d'une longueur supérieure à 1 µm, l'effet de stabilisation d'une émulsion est opéré par la formation d'un réseau de fibrilles enchevêtrées à l'interface eau/huile, ce qui génère des émulsions comprenant des gouttes de grande taille qui sont retrouvées sous la forme d'une pluralité d'agrégats de gouttes en suspension. Les émulsions résultantes ne sont pas homogènes.However, it turns out that such cellulose fibrils with a length greater than 1 μm do not make it possible to obtain calibrated emulsions of controlled and homogeneous size, and therefore do not allow the feasibility of monodisperse emulsions with reduced organic droplet sizes. In fact, with these cellulose fibrils of a length greater than 1 μm, the stabilizing effect of an emulsion is operated by the formation of a network of entangled fibrils at the water / oil interface, which generates emulsions comprising large drops which are found in the form of a plurality of aggregates of suspended drops. The resulting emulsions are not homogeneous.
L'objectif de l'invention est de proposer de nouvelles compositions du genre émulsion huile dans eau (avantageusement de la famille des émulsions de Pickering), contenant des particules émulsifiantes aptes à stabiliser l'émulsion, avantageusement sans agent tensio-actif et cela de manière particulièrement stable dans le temps.The object of the invention is to propose new compositions of the oil-in-water emulsion type (advantageously from the family of Pickering emulsions), containing emulsifying particles capable of stabilizing the emulsion, advantageously without a surfactant and that of particularly stable way in time.
La présente invention concerne ainsi une composition sous forme d'une émulsion comprenant une phase hydrophobe dispersée dans une phase aqueuse, laquelle composition contient des particules émulsifiantes consistant en des nanocristaux de cellulose de forme allongée, avantageusement encore de forme aciculaire, comportant une longueur comprise entre 25 nm et 1 µm, et une largeur comprise entre 5 et 30 nm.The present invention thus relates to a composition in the form of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase, which composition contains emulsifying particles consisting of elongated cellulose nanocrystals, advantageously still of acicular shape, having a length between 25 nm and 1 μm, and a width between 5 and 30 nm.
Les nanocristaux de cellulose ont fait l'objet de nombreuses études, notamment en vue de caractériser leur morphologie et leur structure cristalline.The cellulose nanocrystals have been the subject of numerous studies, in particular with a view to characterizing their morphology and their crystalline structure.
Cependant, à la connaissance des inventeurs, de tels nanocristaux de cellulose n'ont jamais été utilisés en tant que composés émulsifiant / émulsionnant pour la stabilisation d'émulsions.However, to the inventors' knowledge, such cellulose nanocrystals have never been used as emulsifier / emulsifier compounds for the stabilization of emulsions.
Or, tel que démontré dans les exemples suivants, une telle composition s'avère particulièrement stable dans le temps, bien qu'exempte de tensio-actifs. Cette émulsion résiste en plus à des traitements thermiques, aussi bien de type congélation que de type chauffage.However, as demonstrated in the following examples, such a composition is particularly stable over time, although free of surfactants. This emulsion resists in addition to heat treatments, both freeze type heating type.
D'autres caractéristiques avantageuses, pouvant être prises en combinaison ou indépendamment les unes des autres, sont détaillées ci-dessous :
- les nanocristaux de cellulose vérifient les caractéristiques suivantes : une longueur comprise entre 100 nm et 1 µm, et une largeur comprise entre 5 et 20 nm ;
- les nanocristaux de cellulose ont un rapport longueur/largeur supérieur à 1 et inférieur à 100, et de préférence compris entre 10 et 55 ;
- les nanocristaux de cellulose ont une densité de charges de surface maximale de 0,5 e.nm-2, et de préférence une densité de charges de surface maximale de 0,31 e.nm-2, e correspondant à une charge élémentaire ; selon un premier mode de réalisation, les nanocristaux de cellulose comportent une surface chargée, avantageusement des charges de surface négatives, avec une densité de charges de surface comprise entre 0,01 e.nm-2 et 0,31 e.nm-2 ; selon un second mode de réalisation, les nanocristaux de cellulose ont une surface neutre, la densité de charges de surface étant inférieure ou égale à 0,01 e.nm-2 ;
- les nanocristaux de cellulose comportent, en surface, des groupements hydrophobes.
- the cellulose nanocrystals satisfy the following characteristics: a length of between 100 nm and 1 μm, and a width of between 5 and 20 nm;
- the cellulose nanocrystals have a length / width ratio greater than 1 and less than 100, and preferably between 10 and 55;
- the cellulose nanocrystals have a maximum surface charge density of 0.5 e.nm -2 , and preferably a maximum surface charge density of 0.31 e.nm -2 , e corresponding to an elementary charge; according to a first embodiment, the cellulose nanocrystals comprise a charged surface, advantageously negative surface charges, with a surface charge density of between 0.01 e.nm -2 and 0.31 e.nm -2 ; according to a second embodiment, the cellulose nanocrystals have a neutral surface, the density of surface charges being less than or equal to 0.01 e.nm -2 ;
- the cellulose nanocrystals comprise, on the surface, hydrophobic groups.
La présente invention porte également sur l'utilisation de nanocristaux de cellulose tels que définis ci-dessus, pour stabiliser une émulsion comprenant une phase hydrophobe dispersée dans une phase aqueuse.The present invention also relates to the use of cellulose nanocrystals as defined above, for stabilizing an emulsion comprising a hydrophobic phase dispersed in an aqueous phase.
L'invention concerne également le procédé pour la fabrication d'une composition sous forme d'émulsion définie ci-dessus, comprenant les étapes suivantes :
- (a) la fourniture de nanocristaux de cellulose tels que définis ci-dessus, puis
- (b) l'incorporation desdits nanocristaux de cellulose dans la phase aqueuse de ladite composition, de sorte à stabiliser ladite émulsion.
- (a) the supply of cellulose nanocrystals as defined above, then
- (b) incorporating said cellulose nanocrystals into the aqueous phase of said composition, so as to stabilize said emulsion.
Les nanocristaux de cellulose fournis à l'étape (a) sont avantageusement obtenus par un procédé de fabrication à partir d'une cellulose, ledit procédé de fabrication étant choisi parmi l'un des procédés suivants : fractionnement mécanique, hydrolyse chimique ménagée, et dissolution/recristallisationThe cellulose nanocrystals provided in step (a) are advantageously obtained by a manufacturing process from a cellulose, said manufacturing process being chosen from one of the following processes: mechanical fractionation, controlled chemical hydrolysis, and dissolution / recrystallization
Dans ce cas, le procédé de fabrication des nanocristaux de cellulose est avantageusement suivi par un procédé de post-modification desdits nanocristaux de cellulose à l'issue duquel leur densité de charges de surface et/ou leur hydrophobicité sont modifiées.In this case, the process for producing the cellulose nanocrystals is advantageously followed by a method of post-modification of said cellulose nanocrystals at the end of which their surface charge density and / or their hydrophobicity are modified.
Pour une modification de la densité de charge, le procédé de post-modification consiste avantageusement en un procédé d'introduction ou d'hydrolyse des groupements portant les charges de surface, lesquels groupements sont de préférence choisis parmi les groupements sulfonate, carboxylate, phosphate, phosphonate et sulfate.For a modification of the charge density, the post-modification process advantageously consists of a process for introducing or hydrolyzing the groups carrying the surface charges, which groups are preferably chosen from sulphonate, carboxylate and phosphate groups, phosphonate and sulfate.
Selon un premier mode de réalisation préféré, le procédé de fabrication consiste en un procédé d'hydrolyse acide ménagée de la cellulose par l'acide sulfurique, pour obtenir des nanocristaux de cellulose munis de groupements sulfate en surface ; et le procédé de post-modification optionnel consiste en un procédé d'hydrolyse contrôlée desdits groupements sulfate.According to a first preferred embodiment, the manufacturing process consists of a process for the controlled acid hydrolysis of cellulose with sulfuric acid, to obtain cellulose nanocrystals provided with sulfate groups at the surface; and the optional post-modification process consists of a controlled hydrolysis process of said sulfate groups.
Selon un second mode de réalisation préféré, le procédé de fabrication consiste en un procédé d'hydrolyse acide ménagée de la cellulose par l'acide chlorhydrique ; et le procédé de post-modification optionnel consiste en un procédé de post-sulfatation desdits nanocristaux de cellulose.According to a second preferred embodiment, the manufacturing process consists of a process for the mild acid hydrolysis of cellulose with hydrochloric acid; and the method of Optional post-modification consists of a post-sulfation process of said cellulose nanocrystals.
Tel qu'évoqué ci-dessus, la composition selon l'invention consiste en composition sous forme d'une émulsion comprenant une phase hydrophobe dispersée dans une phase aqueuse, et contenant des particules émulsifiantes (ou autrement dit « particules émulsionnantes ») consistant en des nanocristaux de cellulose.As mentioned above, the composition according to the invention consists of a composition in the form of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase, and containing emulsifying particles (or in other words "emulsifying particles") consisting of cellulose nanocrystals.
Par « émulsion », on entend un mélange, macroscopiquement homogène mais microscopiquement hétérogène, de deux phases liquides non miscibles."Emulsion" means a mixture, macroscopically homogeneous but microscopically heterogeneous, of two immiscible liquid phases.
En l'occurrence, l'émulsion selon l'invention est du genre « huile dans eau », c'est-à-dire que (i) la phase dispersante est une phase aqueuse et (ii) la phase dispersée est une phase organique (hydrophobe ou huileuse). Une telle émulsion est encore désignée couramment par le sigle « H/E ».In this case, the emulsion according to the invention is of the type "oil in water", that is to say that (i) the dispersing phase is an aqueous phase and (ii) the dispersed phase is an organic phase (hydrophobic or oily). Such an emulsion is still commonly referred to as "O / W".
Pour assurer sa stabilité, l'émulsion selon l'invention contient ainsi des nanocristaux de cellulose.To ensure its stability, the emulsion according to the invention thus contains cellulose nanocrystals.
Les nanocristaux de cellulose sont connus de l'art antérieur, souvent sous la dénomination de « whiskers » de cellulose ou de « nanowiskers » de cellulose.Cellulose nanocrystals are known from the prior art, often under the name of "whiskers" of cellulose or "nanowiskers" of cellulose.
De tels nanocristaux de cellulose peuvent être issus de diverses sources : végétale (e.g. pulpe de bois, coton ou algues), animale (e.g. tunicier), bactérienne, cellulose régénérée ou cellulose mercerisée. Ils sont par exemple décrits dans le document
Plus précisément, les nanocristaux de cellulose sont des particules solides hautement cristallines.More specifically, cellulose nanocrystals are highly crystalline solid particles.
Ces nanocristaux de cellulose sont dépourvus, ou au moins pratiquement dépourvus, de partie amorphe. Ils présentent de préférence un taux de cristallinité d'au moins 60%, et de préférence compris entre 60% et 95% (voir par exemple Elazzouzi-Hafraoui et al., 2008 précité).These cellulose nanocrystals are lacking, or at least substantially free, of amorphous part. They preferably have a degree of crystallinity of at least 60%, and preferably between 60% and 95% (see for example Elazzouzi-Hafraoui et al., 2008 cited above).
Pour la composition selon l'invention, les nanocristaux de cellulose ont une forme allongée, c'est-à-dire avantageusement un rapport longueur/largeur supérieur à 1.For the composition according to the invention, the cellulose nanocrystals have an elongated shape, that is to say advantageously a length / width ratio greater than 1.
De préférence encore, ces nanocristaux de cellulose ont une forme aciculaire, c'est-à-dire une forme linéaire et pointue rappelant une aiguille.More preferably, these cellulose nanocrystals have an acicular shape, that is to say a linear and pointed shape reminding a needle.
Cette morphologie peut être observée par exemple par microscopie électronique, en particulier par microscopie électronique en transmission (ou « MET »).This morphology can be observed for example by electron microscopy, in particular by transmission electron microscopy (or "MET").
Toujours dans la composition selon l'invention, ces nanocristaux de cellulose comportent les caractéristiques dimensionnelles suivantes : (i) une longueur comprise entre 25 nm et 1 µm, et (ii) une largeur comprise entre 5 et 30 nm.Still in the composition according to the invention, these cellulose nanocrystals comprise the following dimensional characteristics: (i) a length of between 25 nm and 1 μm, and (ii) a width of between 5 and 30 nm.
Par « longueur », on entend la plus grande dimension des nanocristaux, séparant deux points situés aux extrémités de leur axe longitudinal respectif.By "length" is meant the largest dimension of the nanocrystals, separating two points located at the ends of their respective longitudinal axis.
Par « largeur », on entend la dimension mesurée le long des nanocristaux, perpendiculairement à leur axe longitudinal respectif et correspondant à leur section maximale.By "width" is meant the dimension measured along the nanocrystals, perpendicular to their respective longitudinal axis and corresponding to their maximum section.
Dans des modes de réalisation préférés, les nanoparticules de cellulose forment une population relativement homogène de nanocristaux dont les valeurs expérimentales de longueur suivent une distribution Gaussienne centrée sur la valeur de longueur assignée pour ladite population de nanocristaux. Dans ces modes de réalisation préférés, on peut utiliser par exemple des nanocristaux de cellulose d'une « seule taille déterminée », comme cela est illustré dans les exemples.In preferred embodiments, the cellulose nanoparticles form a relatively homogeneous population of nanocrystals whose experimental length values follow a Gaussian distribution centered on the assigned length value for said nanocrystal population. In these preferred embodiments, for example, cellulose nanocrystals of a "single determined size" can be used, as illustrated in the examples.
En pratique, la morphologie et les dimensions des nanocristaux peuvent être déterminées en utilisant différentes techniques d'imagerie comme la microscopie électronique à transmission (MET) ou la microscopie à force atomique (AFM), la diffusion des rayons X ou des neutrons aux petits angles (respectivement SAXS pour « Small-Angle X-ray Scattering » et SANS pour « Small-Angle Neutron Scattering ») ou encore la diffusion dynamique de la lumière (DDL).In practice, the morphology and dimensions of nanocrystals can be determined using various imaging techniques such as transmission electron microscopy (TEM) or atomic force microscopy (AFM), X-ray scattering or small-angle neutrons (respectively SAXS for "Small-Angle X-ray Scattering" and SANS for "Small-Angle Neutron Scattering") or dynamic light scattering (DDL).
Selon un mode préféré de réalisation, les nanocristaux de cellulose présentent les dimensions suivantes : (i) une longueur comprise entre 100 nm et 1 µm, et (ii) une largeur comprise entre 5 et 20 nm.According to a preferred embodiment, the cellulose nanocrystals have the following dimensions: (i) a length of between 100 nm and 1 μm, and (ii) a width of between 5 and 20 nm.
Avantageusement encore, les nanocristaux de cellulose ont un rapport longueur/largeur supérieur à 1 et inférieur à 100, de préférence compris entre 10 et 55.Advantageously, the cellulose nanocrystals have a length / width ratio greater than 1 and less than 100, preferably between 10 and 55.
Un rapport longueur/largeur supérieur à 1 et inférieur à 100 englobe les rapports longueur/largeur d'au moins 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 et 99.A length / width ratio greater than 1 and less than 100 includes length / width ratios of at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 and 99.
Un rapport longueur/largeur compris entre 10 et 55 englobe les rapports longueur/largeur choisis parmi 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53 et 54.A length / width ratio of 10 to 55 includes length / width ratios selected from 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53 and 54.
Par exemple, les nanocristaux obtenus à partir de la cellulose de coton comportent avantageusement une longueur comprise entre 100 nm et 200 nm, pour une largeur comprise entre 12 et 15 nm. Le rapport longueur/largeur est compris avantageusement entre 7 et 17, et de préférence entre 10 et 13.For example, the nanocrystals obtained from cotton cellulose advantageously have a length of between 100 nm and 200 nm, for a width of between 12 and 15 nm. The length / width ratio is advantageously between 7 and 17, and preferably between 10 and 13.
Selon un autre exemple, les nanocristaux peuvent être obtenus à partir d'une cellulose bactérienne. De tels nanocristaux (connus sous l'appellation de « nanocristaux de cellulose bactérienne » ou « BCN ») comportent avantageusement une longueur comprise entre 600 nm et 1 µm, pour une largeur comprise entre 12 et 17 nm. Le rapport longueur/largeur est compris avantageusement entre 35 et 83, de préférence entre 45 et 55.In another example, the nanocrystals can be obtained from a bacterial cellulose. Such nanocrystals (known under the name of "bacterial cellulose nanocrystals" or "BCN") advantageously comprise a length of between 600 nm and 1 μm, for a width of between 12 and 17 nm. The length / width ratio is advantageously between 35 and 83, preferably between 45 and 55.
Pour optimiser la stabilité des émulsions de Pickering, les nanocristaux de cellulose sont avantageusement choisis en fonction de leurs caractéristiques de surface, tenant compte notamment de (i) l'aspect électrostatique et/ou (ii) de l'hydrophobicité ou de l'hydrophilicité.To optimize the stability of Pickering emulsions, the cellulose nanocrystals are advantageously chosen according to their surface characteristics, taking into account in particular (i) the electrostatic appearance and / or (ii) hydrophobicity or hydrophilicity .
Concernant l'aspect électrostatique de surface, les nanocristaux de cellulose stabilisant l'émulsion ont avantageusement une densité de charges de surface maximale de 0,5 e.nm-2, et de préférence une densité de charges de surface maximale de 0,31 e.nm-2. On note que « e » correspond à une charge élémentaire.With regard to the electrostatic surface appearance, the emulsion stabilizing cellulose nanocrystals advantageously have a maximum surface charge density of 0.5 e.nm -2 , and preferably a maximum surface charge density of 0.31 e .nm -2 . We note that "e" corresponds to an elementary charge.
La densité de charge en surface et la force ionique de la phase aqueuse sont avantageusement adaptées l'une par rapport à l'autre.The surface charge density and the ionic strength of the aqueous phase are advantageously adapted relative to one another.
Avantageusement, cette densité de charge de surface est déterminée par dosage conductimétrique ; un mode de réalisation particulier est décrit ci-après dans la partie Exemples.Advantageously, this surface charge density is determined by conductimetric assay; a particular embodiment is described below in the Examples section.
Plus précisément et selon un mode de réalisation, les nanocristaux de cellulose comportent une surface chargée, avec une densité de charges de surface comprise entre 0,01 e.nm-2 et 0,31 e.nm-2.More precisely and according to one embodiment, the cellulose nanocrystals comprise a charged surface, with a surface charge density of between 0.01 e.nm -2 and 0.31 e.nm -2 .
Comme cela est décrit dans les exemples, la densité désirée de charges de surface peut être obtenue par un contrôle du degré de sulfatation des nanocristaux. Le degré de sulfatation des nanocristaux peut être contrôlé en soumettant les nanocristaux de cellulose à un traitement de sulfatation et, si nécessaire, à un traitement subséquent de désulfatation.As described in the examples, the desired density of surface charges can be obtained by controlling the degree of sulfation of the nanocrystals. The degree of sulfation of the nanocrystals can be controlled by subjecting the cellulose nanocrystals to a sulfation treatment and, if necessary, subsequent desulfation treatment.
La demanderesse a montré qu'une émulsion de Pickering stable est obtenue lorsqu'on utilise des nanocristaux de cellulose pratiquement non chargés.Applicant has shown that a stable Pickering emulsion is obtained when substantially uncharged cellulose nanocrystals are used.
La demanderesse a également montré qu'au-delà de 0,31 e.mm-2, la stabilité de l'émulsion de Pickering est très significativement altérée. La demanderesse a montré que des nanocristaux de cellulose possédant une valeur de densité de charge trop grande présentent une surface trop hydrophile et sont retrouvés en grande quantité en suspension dans la phase aqueuse au lieu d'être localisés à l'interface huile/eau pour stabiliser l'émulsion.The Applicant has also shown that beyond 0.31 e.mm -2 , the stability of the Pickering emulsion is very significantly altered. The Applicant has shown that cellulose nanocrystals having an excessively high charge density value have an excessively hydrophilic surface and are found in large amounts in suspension in the aqueous phase instead of being located at the oil / water interface to stabilize the emulsion.
Dans ce cas, les nanocristaux de cellulose comportent avantageusement des charges de surface négatives, qui sont avantageusement portées par des groupements anioniques en surface.In this case, the cellulose nanocrystals advantageously comprise negative surface charges, which are advantageously carried by anionic groups on the surface.
Les groupements anioniques des nanocristaux de cellulose sont choisis par exemple parmi les groupements sulfonate, les groupements carboxylate, les groupements phosphate, les groupements phosphonate et les groupements sulfate.The anionic groups of the cellulose nanocrystals are chosen, for example, from sulphonate groups, carboxylate groups, phosphate groups, phosphonate groups and sulphate groups.
La transposition d'une valeur de degré de substitution (DS) à la valeur correspondante de densité de charges de surface (e.mm-2) est directe, dès lors que le nombre de charges du groupement chimique considéré est connu. A titre illustratif, pour les groupements sulfate, qui portent une charge unique, la valeur de DS (nombre de groupes sulfate par unité de surface) est identique à la valeur de densité de charges de surface (nombre de charges par unité de surface identique).The transposition of a degree of substitution value (DS) to the corresponding value of surface charge density (e.mm -2 ) is direct, since the number of charges of the considered chemical group is known. As an illustration, for sulphate groups, which carry a single charge, the value of DS (number of sulphate groups per unit area) is identical to the value of density of surface charges (number of charges per unit of identical surface) .
En d'autres termes, ces nanocristaux de cellulose ont un degré de substitution (DS) compris entre 10-3 et 10-2 e/nm2, ou un degré de substitution en surface (DSs) compris entre DS/0,19 à DS/0,4, selon la morphologie des nanocristaux utilisés.In other words, these cellulose nanocrystals have a degree of substitution (DS) of between 10 -3 and 10 -2 e / nm 2 , or a degree of surface substitution (DSs) of between DS / 0.19 at DS / 0.4, according to the morphology of the nanocrystals used.
Selon un autre mode de réalisation, les nanocristaux de cellulose ont une surface neutre. Dans ce cas, la densité de charges de surface est avantageusement inférieure ou égale à 0,01 e.nm-2.According to another embodiment, the cellulose nanocrystals have a neutral surface. In this case, the density of surface charges is advantageously less than or equal to 0.01 e.nm -2 .
En pratique, la densité de charge des nanocristaux de cellulose est avantageusement choisie en fonction de la force ionique de la phase aqueuse de la composition.In practice, the charge density of the cellulose nanocrystals is advantageously chosen as a function of the ionic strength of the aqueous phase of the composition.
Les nanocristaux de cellulose utilisés selon l'invention consistent avantageusement en des nanocristaux de cellulose qui n'ont pas subi de traitement d'hydrophobisation. Cela englobe les nanocristaux de cellulose dont les groupes hydroxyle n'ont pas été fonctionnalisés par des atomes ou des groupes hydrophobes. Typiquement, cela englobe les nanocristaux qui n'ont pas subi de traitement d'hydrophobisation par estérification de groupes hydroxyle par des acides organiques.The cellulose nanocrystals used according to the invention advantageously consist of cellulose nanocrystals which have not undergone any hydrophobization treatment. This includes cellulose nanocrystals whose hydroxyl groups have not been functionalized by atoms or hydrophobic groups. Typically, this includes nanocrystals which have not undergone hydrophobicization treatment by esterification of hydroxyl groups with organic acids.
Dans des modes de réalisation avantageux, les nanocristaux de cellulose qui sont utilisés pour obtenir l'émulsion de Pickering ne subissent aucun traitement chimique postérieur à leur obtention, autre qu'un traitement de désulfatation ou de sulfatation. Notamment, on utilise préférentiellement des nanocristaux de cellulose qui n'ont pas été fonctionnalisés ou greffés avec des groupes permettant leur réticulation subséquente, par exemple par des groupes du type méthacrylate ou diméthacrylate. Egalement, on utilise préférentiellement des nanocristaux de cellulose qui n'ont pas été fonctionnalisés ou greffés par des molécules polymères, telles qu'un polyéthylène glycol, un poly(hydroxyester) ou encore un polystyrène.In advantageous embodiments, the cellulose nanocrystals that are used to obtain the Pickering emulsion do not undergo any subsequent chemical processing, other than a desulfation or sulfation treatment. In particular, cellulose nanocrystals which have not been functionalized or grafted with groups allowing their subsequent crosslinking, for example by groups of the methacrylate or dimethacrylate type, are preferably used. Also, cellulose nanocrystals which have not been functionalized or grafted with polymer molecules, such as polyethylene glycol, a poly (hydroxyester) or a polystyrene, are preferably used.
La demanderesse a également montré que la stabilité de l'émulsion de Pickering peut être accrue en utilisant une phase aqueuse ayant une force ionique minimale déterminée.The Applicant has also shown that the stability of the Pickering emulsion can be increased by using an aqueous phase having a determined minimum ionic strength.
En l'occurrence, une stabilité maximale de l'émulsion de Pickering est obtenue pour une valeur de force ionique correspondant à une concentration finale de NaCl de 0,02 M dans ladite émulsion.In this case, maximum stability of the Pickering emulsion is obtained for an ionic strength value corresponding to a final NaCl concentration of 0.02 M in said emulsion.
Sans vouloir être lié par une quelconque théorie, le demandeur pense que la valeur seuil de force ionique de la phase aqueuse à partir de laquelle une stabilité optimale de l'émulsion est obtenue est celle pour laquelle les charges (contre-ions) présentes dans la phase aqueuse neutralisent les charges (ions) présentes sur les nanocristaux.Without wishing to be bound by any theory, the applicant believes that the ionic strength threshold value of the aqueous phase from which optimal stability of the emulsion is obtained is that for which the charges (counter-ions) present in the aqueous phase neutralize the charges (ions) present on the nanocrystals.
Comme cela est montré dans les exemples, la présence de contre-ions en excès n'influe pas significativement sur les propriétés de stabilité de l'émulsion. Pour un excès massif de contre-ions, qui n'a pas été atteint dans les conditions opératoires des exemples, on peut présager une altération de la stabilité de l'émulsion, du fait d'une précipitation des nanocristaux.As shown in the examples, the presence of excess counterions does not significantly affect the stability properties of the emulsion. For a massive excess of counter-ions, which has not been reached under the operating conditions of the examples, it is possible to predict an alteration of the stability of the emulsion, due to a precipitation of the nanocrystals.
A titre indicatif, selon un mode de réalisation particulier, pour une composition comportant une force ionique inférieure à la force ionique équivalente à 10 mM de NaCl, les nanocristaux de cellulose comportent avantageusement une densité de charges de surface maximale de 0,03 e.nm-2.As an indication, according to a particular embodiment, for a composition having an ionic strength less than the ionic strength equivalent to 10 mM NaCl, the cellulose nanocrystals advantageously have a maximum surface charge density of 0.03 e.nm -2 .
Pour une composition comportant une force ionique supérieure à la force ionique équivalente à 10 mM de NaCl, la densité de charges de surface portée par les nanocristaux de cellulose semble ne plus être un paramètre pertinent pour la stabilisation effective de l'émulsion.For a composition having an ionic strength greater than the ionic strength equivalent to 10 mM NaCl, the surface charge density carried by the cellulose nanocrystals does not seem to be a relevant parameter for the effective stabilization of the emulsion.
Une force ionique supérieure à la force ionique équivalente à 10 mM de NaCl inclut une force ionique supérieure à 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 275, 280, 290, 300, 310, 315, 320, 325, 330, 335, 340, 345, 350, 360, 370, 375, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, ou supérieure à 500 mM de NaCl. De préférence, la force ionique est inférieure à une force ionique équivalent à 3 M de NaCl.An ionic strength greater than the ionic strength equivalent to 10 mM NaCl includes an ionic strength greater than 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 275, 280, 290, 300, 310, 315, 320, 325, 330, 335, 340, 345, 350, 360, 370, 375, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or greater than 500 mM NaCl. Preferably, the ionic strength is less than an ionic strength equivalent to 3 M NaCl.
Les résultats des exemples montrent que, dans certains modes de réalisation d'une émulsion selon l'invention, la stabilité desdites émulsions est déjà maximale pour une force ionique de la composition de 20 mM de NaCl, et le niveau de stabilité de l'émulsion étant maintenu pratiquement inchangé pour toutes les valeurs de force ionique testées, c'est-à-dire au moins jusqu'à une valeur de force ionique équivalent à la force ionique de 0,5 M de NaCl.The results of the examples show that, in certain embodiments of an emulsion according to the invention, the stability of said emulsions is already maximal for an ionic strength of the composition of 20 mM NaCl, and the level of stability of the emulsion being kept substantially unchanged for all ionic strength values tested, i.e. at least up to an ionic strength value equivalent to the ionic strength of 0.5 M NaCl.
De manière alternative ou complémentaire, toujours pour optimiser la stabilisation d'émulsions, les nanocristaux de cellulose comportent des groupements hydrophobes en surface.Alternatively or additionally, still to optimize the stabilization of emulsions, the cellulose nanocrystals comprise hydrophobic groups on the surface.
La densité de groupements hydrophobes en surface peut être un paramètre intéressant pour tenir compte de la tension interfaciale (nature de la phase aqueuse et de la phase huileuse).The density of hydrophobic groups at the surface may be an interesting parameter to take account of the interfacial tension (nature of the aqueous phase and the oily phase).
De tels groupements hydrophobes sont choisis avantageusement parmi les groupements acétyle, alkyle, aryle, phényle, benzyle, hydroxybutyle, hydroxypropyle, polycaprolactone (ou PCL).Such hydrophobic groups are advantageously chosen from acetyl, alkyl, aryl, phenyl, benzyl, hydroxybutyl, hydroxypropyl and polycaprolactone (or PCL) groups.
Les nanocristaux de cellulose sont généralement incorporés dans la phase aqueuse de la composition.The cellulose nanocrystals are generally incorporated into the aqueous phase of the composition.
Selon un mode de réalisation préféré, la composition d'émulsion de Pickering est stabilisée uniquement par les nanocristaux de cellulose, sans ajout d'autres composés émulsifiant ou stabilisant.According to a preferred embodiment, the Pickering emulsion composition is stabilized solely by the cellulose nanocrystals, without the addition of other emulsifying or stabilizing compounds.
Selon un mode de réalisation préféré, la composition d'émulsion de Pickering ne comprend aucune particule solide, non fonctionnalisée ou fonctionnalisée, autre que les nanocristaux de cellulose.In a preferred embodiment, the Pickering emulsion composition does not include any solid, non-functionalized, or functionalized particles other than cellulose nanocrystals.
De manière alternative, la composition est stabilisée par les nanocristaux de cellulose, rapportés en combinaison avec au moins un autre composé ayant des propriétés émulsifiantes et/ou des propriétés stabilisantes, par exemple avec ou sans agent(s) tensio-actif(s).Alternatively, the composition is stabilized by the cellulose nanocrystals, reported in combination with at least one other compound having emulsifying properties and / or stabilizing properties, for example with or without surfactant (s).
Par exemple, la composition de Pickering selon l'invention peut contenir du CTAB (bromure d'hexadécyltriméthylammonium).For example, the Pickering composition of the invention may contain CTAB (hexadecyltrimethylammonium bromide).
La composition comprend avantageusement de 0,035% à 2% en poids, de préférence encore de 0,05% à 1% en poids, de nanocristaux de cellulose par rapport au poids total de ladite composition.The composition advantageously comprises from 0.035% to 2% by weight, more preferably from 0.05% to 1% by weight, of cellulose nanocrystals relative to the total weight of said composition.
Cette proportion massique en nanocristaux de cellulose peut être évaluée par exemple par extrait sec de la phase aqueuse ou par dosage des sucres après hydrolyse.This mass proportion of cellulose nanocrystals may be evaluated, for example, by dry extract of the aqueous phase or by determination of the sugars after hydrolysis.
Il est montré selon l'invention qu'une quantité de nanocristaux de cellulose suffisante pour l'obtention d'un taux de recouvrement d'au moins 60% est préféré pour la préparation d'une composition d'émulsion de Pickering.
En particulier, lorsqu'on utilise une masse de nanoparticules trop faible par rapport au volume d'huile, il est susceptible de se produire une coalescence des gouttelettes de la phase hydrophobe de manière à tendre vers un recouvrement minimum de 60%.It is shown according to the invention that a sufficient amount of cellulose nanocrystals to obtain a coverage ratio of at least 60% is preferred for the preparation of a Pickering emulsion composition.
In particular, when a mass of nanoparticles that is too small relative to the volume of oil is used, it is likely to coalesce the droplets of the hydrophobic phase so as to tend towards a minimum coverage of 60%.
Au sens de la présente description, le « taux de recouvrement » par des nanocristaux de cellulose représente la proportion de la surface des gouttelettes de phase hydrophobe dispersées dans la phase aqueuse, à l'interface huile/eau, qui est recouverte par les nanocristaux de cellulose.For the purposes of the present description, the "recovery rate" by cellulose nanocrystals represents the proportion of the surface of the hydrophobic phase droplets dispersed in the aqueous phase, at the oil / water interface, which is covered by the nanocrystals of cellulose.
Le taux de recouvrement « C », qui est le rapport entre (i) la surface de nanocristaux de cellulose présents dans la composition d'émulsion susceptible de se stabiliser à l'interface phase interne hydrophobe/phase continue hydrophile et (ii) la surface totale des gouttelettes de phase hydrophobe dans ladite composition d'émulsion, est calculé selon la formule (I) suivante : 
- Sp représente la surface de nanocristaux de cellulose susceptible de se stabiliser à l'interface présents dans la composition d'émulsion, et
- Sd représente la surface totale des gouttelettes de phase hydrophobe dans la composition d'émulsion.
- S p represents the surface of interfacially stabilizing cellulose nanocrystals present in the emulsion composition, and
- S d represents the total area of the hydrophobic phase droplets in the emulsion composition.
La surface des nanocristaux est assimilée à une surface à un seul plan, en prenant l'hypothèse que les nanocristaux sont alignés sur ladite surface en un ruban plat.The surface of the nanocrystals is likened to a single-plane surface, assuming that the nanocrystals are aligned on said surface in a flat ribbon.
En conséquence, la valeur de surface des nanocristaux peut être calculée selon la formule (II) suivante : 
- Sp représente la surface de nanocristaux de cellulose susceptible de se stabiliser à l'interface présents dans la composition d'émulsion,
- Np signifie le nombre de nanocristaux de cellulose présentes dans la phase aqueuse,
- L signifie la longueur des nanocristaux de cellulose ,
- l signifie la largeur des nanocristaux de cellulose
- h signifie la hauteur des nanocristaux de cellulose
- mp signifie la masse de nanocristaux de cellulose, et
- p signifie la densité des nanocristaux de cellulose
- S p represents the surface of interfacially stabilizing cellulose nanocrystals present in the emulsion composition,
- N p is the number of cellulose nanocrystals present in the aqueous phase,
- L is the length of the cellulose nanocrystals,
- l means the width of the cellulose nanocrystals
- h means the height of the cellulose nanocrystals
- m p is the mass of cellulose nanocrystals, and
- p is the density of cellulose nanocrystals
La surface des gouttelettes est la surface à l'interface huile/eau, qui a été calculée pour chaque diamètre moyen de gouttelettes selon D(3,2).The area of the droplets is the area at the oil / water interface, which has been calculated for each average droplet diameter according to D (3,2).
En conséquence, la valeur de surface des gouttelettes peut être calculée selon la formule (III) suivante : 
- Ng signifie le nombre de gouttes présentes dans l'émulsion
- Sd signifie la valeur de surface des gouttelettes de phase hydrophobe,
- R signifie le rayon moyen des gouttelettes, et
- Voil signifie le volume total de la phase interne hydrophobe.
- Ng means the number of drops present in the emulsion
- S d means the surface value of the hydrophobic phase droplets,
- R is the mean radius of the droplets, and
- V oil means the total volume of the hydrophobic internal phase.
La valeur finale du taux de recouvrement « C » est calculée selon la formule (I) déjà mentionnée ci-dessus : 
- Sp représente la surface de nanocristaux de cellulose susceptible de se stabiliser à l'interface et présents dans la composition d'émulsion,
- Sd représente la surface totale des gouttelettes de phase hydrophobe dans la composition d'émulsion.
- S p represents the surface of nanocrystals of cellulose capable of stabilizing at the interface and present in the emulsion composition,
- S d represents the total area of the hydrophobic phase droplets in the emulsion composition.
Dans la composition d'émulsion de Pickering, la phase dispersée hydrophobe représente avantageusement moins de 50% en volume par rapport au volume total de la composition.In the Pickering emulsion composition, the hydrophobic dispersed phase advantageously represents less than 50% by volume relative to the total volume of the composition.
La phase hydrophobe représente avantageusement de 5% à 45% en volume par rapport au poids total de la composition.The hydrophobic phase advantageously represents from 5% to 45% by volume relative to the total weight of the composition.
Tel que décrit ci-dessous, la phase hydrophobe est choisie parmi les huiles végétales, les huiles animales, les huiles minérales, les huiles de synthèse, les solvants organiques hydrophobes et les polymères liquides hydrophobes.As described below, the hydrophobic phase is selected from vegetable oils, animal oils, mineral oils, synthetic oils, hydrophobic organic solvents and hydrophobic liquid polymers.
La composition d'émulsion de Pickering selon l'invention peut contenir encore tout autre composé approprié à son utilisation ou destination finale.The Pickering emulsion composition according to the invention may also contain any other compound suitable for its use or final destination.
Cette composition d'émulsion de Pickering peut ainsi être adaptée à l'application choisie avantageusement parmi les compositions alimentaires, les compositions cosmétiques, les compositions pharmaceutiques et les compositions phytosanitaires.This Pickering emulsion composition can thus be adapted to the application advantageously chosen from food compositions, cosmetic compositions, pharmaceutical compositions and phytosanitary compositions.
De façon connue et en fonction de son application, la composition peut contenir par exemple, sans être aucunement limitatif, des principes actifs et des adjuvants tels que des conservateurs, des gélifiants, des solvants, des matières colorantes, etc.In known manner and depending on its application, the composition may contain, for example, without being limiting, active principles and adjuvants such as preservatives, gelling agents, solvents, dyestuffs, etc.
La phase hydrophobe est choisie parmi les huiles végétales, les huiles animales, les huiles minérales, les huiles de synthèse, les solvants organiques hydrophobes et les polymères liquides hydrophobes.The hydrophobic phase is chosen from vegetable oils, animal oils, mineral oils, synthetic oils, hydrophobic organic solvents and hydrophobic liquid polymers.
La phase hydrophobe peut être choisie parmi un alcane ou un cycloalcane, substitué ou non substitué.The hydrophobic phase may be selected from a substituted or unsubstituted alkane or cycloalkane.
Pour la phase hydrophobe, un alcane ayant plus de 5 atomes de carbone englobe les alcanes ayant plus de 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 ou plus de 17 atomes de carbone, c'est-à-dire notamment, selon la nomenclature conventionnelle, les alcanes en C6-C18 et qui sont de formule Cn H2n+2. Lesdits alcanes peuvent être linéaires ou ramifiés.For the hydrophobic phase, an alkane having more than 5 carbon atoms includes alkanes having more than 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or more than 17 carbon atoms. that is to say, according to the conventional nomenclature, C 6 -C 18 alkanes and which are of formula C n H 2n + 2 . Said alkanes may be linear or branched.
Lesdits alcanes englobent les alcanes linéaires, cycliques ou ramifiés, des types hexane, heptane, octane, nonane, décane, undécane, dodécane, tridécane, tétradécane, pentadécane, hexadécane, heptadécane et octadécane.Said alkanes include linear, cyclic or branched alkanes of the hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane types.
Les alcanes substitués englobent les alcanes linéaires ou ramifiés ci-dessus dont au moins un atome d'hydrogène est substitué par un halogène choisi parmi le chlore, le brome, l'iode ou le fluor. La substitution d'au moins un atome d'hydrogène, englobe la substitution de 2, 3, 4 ou 5 atomes d'hydrogene.The substituted alkanes include the above straight or branched alkanes of which at least one hydrogen atom is substituted with a halogen selected from chlorine, bromine, iodine or fluorine. The substitution of at least one hydrogen atom includes the substitution of 2, 3, 4 or 5 hydrogen atoms.
Dans certains modes de réalisation, ledit cycloalcane est un cyclohexane non substitué ou substitué. Le cyclohexane peut être substitué par 1, 2, 3 ou 4 atomes d'halogène choisi parmi le chlore, le brome, l'iode ou le fluor.In some embodiments, said cycloalkane is unsubstituted or substituted cyclohexane. The cyclohexane may be substituted with 1, 2, 3 or 4 halogen atoms selected from chlorine, bromine, iodine or fluorine.
La phase hydrophobe peut encore comprendre un mélange de tels alcanes, par exemple sous la forme d'une huile de paraffine.The hydrophobic phase may further comprise a mixture of such alkanes, for example in the form of a paraffin oil.
Dans certains modes de réalisation, la phase hydrophobe comprend un ou plusieurs monomères hydrophobes polymérisables, d'un type connu.In some embodiments, the hydrophobic phase comprises one or more polymerizable hydrophobic monomers of a known type.
Dans d'autres modes de réalisation, la phase hydrophobe consiste essentiellement en une composition d'un monomère hydrophobe ou d'un mélange de monomères hydrophobes. A titre illustratif, la phase hydrophobe peut consister essentiellement en une composition de monomères de styrène.In other embodiments, the hydrophobic phase consists essentially of a composition of a hydrophobic monomer or a mixture of hydrophobic monomers. As an illustration, the hydrophobic phase may consist essentially of a styrene monomer composition.
Par « phase hydrophile » ou « phase aqueuse », on entend un liquide immiscible avec la phase hydrophobe. On utilise de préférence une phase hydrophile miscible avec l'eau. La phase hydrophile peut être de l'eau, comme cela est illustré dans les exemples.The term "hydrophilic phase" or "aqueous phase" means an immiscible liquid with the hydrophobic phase. A hydrophilic phase which is miscible with water is preferably used. The hydrophilic phase may be water, as illustrated in the examples.
La phase hydrophile peut être un solvant hydrophile, de préférence un solvant portant des groupes hydroxyle, tels que des glycols. Pour la phase hydrophile, les glycols englobent le glycérol et les polyéthylène glycols.
La phase hydrophile peut également contenir des agents hydrosolubles texturants, notamment épaississants ou viscosifiants, tels que des polysaccharides (par exemple dextran ou xanthane, ce dernier étant très utilisé dans les applications alimentaires).The hydrophilic phase may be a hydrophilic solvent, preferably a solvent carrying hydroxyl groups, such as glycols. For the hydrophilic phase, the glycols include glycerol and polyethylene glycols.
The hydrophilic phase may also contain water-soluble texturizing agents, in particular thickening or viscosifying agents, such as polysaccharides (for example dextran or xanthan, the latter being widely used in food applications).
La phase hydrophile peut être constituée, en partie ou totalement, par un liquide organique choisi parmi un alcool tel que l'éthanol, ou encore l'acétone.The hydrophilic phase may consist, in part or totally, of an organic liquid selected from an alcohol such as ethanol, or else acetone.
La phase hydrophile peut comprendre un seul liquide ou un mélange de plusieurs liquides.The hydrophilic phase may comprise a single liquid or a mixture of several liquids.
Le procédé pour la fabrication de la composition selon l'invention, comprend avantageusement les étapes suivantes :
- (a) la fourniture de nanocristaux de cellulose tels que définis ci-dessus, puis
- (b) l'incorporation desdits nanocristaux de cellulose dans la phase aqueuse de ladite composition, de sorte à stabiliser ladite émulsion.
- (a) the supply of cellulose nanocrystals as defined above, then
- (b) incorporating said cellulose nanocrystals into the aqueous phase of said composition, so as to stabilize said emulsion.
Les étapes générales pour la fabrication de l'émulsion peuvent être réalisées selon des procédures classiques, notamment employées pour la fabrication d'émulsion de Pickering.The general steps for the manufacture of the emulsion can be carried out according to conventional procedures, especially used for the manufacture of Pickering emulsion.
On peut ainsi par exemple employer une technique d'obtention d'émulsion par ultrasons.For example, a technique for obtaining an ultrasonic emulsion can be used.
En particulier, l'étape d'incorporation des nanocristaux de cellulose dans la phase aqueuse correspond aux étapes mises en oeuvre pour l'incorporation de particules colloïdales lors de la fabrication d'émulsions de Pickering.In particular, the step of incorporating the cellulose nanocrystals in the aqueous phase corresponds to the steps used for the incorporation of colloidal particles during the manufacture of Pickering emulsions.
Les nanocristaux de cellulose fournis à l'étape (a) sont avantageusement obtenus par un procédé de fabrication à partir d'une cellulose.The cellulose nanocrystals provided in step (a) are advantageously obtained by a manufacturing process from a cellulose.
La cellulose est choisie avantageusement parmi l'une au moins des celluloses d'origine suivante : végétale, animale, bactérienne, algale ou régénérée à partir d'une cellulose transformée de sources commerciales.The cellulose is advantageously chosen from at least one of the following celluloses: vegetable, animal, bacterial, algal or regenerated from a cellulose transformed from commercial sources.
La principale source de cellulose est la fibre végétale. La cellulose y est présente comme composante de la paroi cellulaire, sous forme de faisceaux de micro-fibrilles.The main source of cellulose is vegetable fiber. Cellulose is present as a component of the cell wall, in the form of bundles of micro-fibrils.
Une partie de ces micro-fibrilles est composée de cellulose dite « amorphe », alors qu'une seconde partie est constituée de cellulose dite « cristalline ».Part of these micro-fibrils is composed of so-called "amorphous" cellulose, while a second part consists of "crystalline" cellulose.
Les nanocristaux de cellulose sont avantageusement issus de la cellulose cristalline isolée à partir des fibres végétales, par élimination de la partie amorphe de cellulose.The cellulose nanocrystals are advantageously derived from crystalline cellulose isolated from plant fibers, by elimination of the amorphous cellulose part.
Parmi les sources végétales, on peut citer par exemple le coton, le bouleau, le chanvre, la ramie, le lin, l'épicéa.Examples of plant sources are cotton, birch, hemp, ramie, flax, spruce.
Parmi les sources algales de cellulose, on peut citer par exemple Valonia ou Chladophora. Among the algal sources of cellulose, there may be mentioned for example Valonia or Chladophora.
Parmi les sources bactériennes de cellulose, on peut citer Gluconoacetobacter xylinus qui produit du Nata de coco par incubation directement dans du lait de noix de coco.Among the bacterial sources of cellulose, mention may be made of Gluconoacetobacter xylinus which produces Nata de coco by incubation directly in coconut milk.
Parmi les sources animales de cellulose, on peut citer par exemple le tunicier.Among the animal sources of cellulose, there may be mentioned for example the tunicier.
La cellulose peut également être régénérée à partir d'une cellulose transformée de sources commerciales, notamment sous forme de papier.The cellulose can also be regenerated from a commercially-processed cellulose, especially in the form of paper.
On peut citer par exemple du papier de filtration Whatman (marque déposée) pour l'obtention de cellulose de coton.For example, Whatman (registered trademark) filtration paper can be used to obtain cotton cellulose.
La cellulose peut également consister en une cellulose dite « mercerisée » (la mercerisation consiste en un traitement de cellulose généralement à base d'hydroxyde de sodium).The cellulose may also consist of a so-called "mercerized" cellulose (mercerization consists of a treatment of cellulose generally based on sodium hydroxide).
Partant de cette matière première cellulosique, le procédé de fabrication des nanocristaux est avantageusement choisi parmi l'un des procédés suivants : fractionnement mécanique, hydrolyse chimique ménagée, et dissolution/recristallisationStarting from this cellulosic raw material, the process for producing the nanocrystals is advantageously chosen from one of the following processes: mechanical fractionation, controlled chemical hydrolysis, and dissolution / recrystallization
Par « fractionnement mécanique », on entend une opération classique d'homogénéisation haute pression.By "mechanical fractionation" is meant a conventional operation of high pressure homogenization.
Par « hydrolyse chimique ménagée », on entend un traitement par un composé chimique acide de la cellulose, dans des conditions assurant l'élimination de sa partie amorphe.By "controlled chemical hydrolysis" is meant treatment with an acidic chemical compound of cellulose, under conditions ensuring the removal of its amorphous part.
Le composé chimique acide est avantageusement choisi parmi l'acide sulfurique ou l'acide chlorhydrique.The acidic chemical compound is advantageously chosen from sulfuric acid or hydrochloric acid.
Tel que décrit dans les exemples ci-après, selon le type d'acide, la température et le temps d'hydrolyse, la charge de surface peut être modulée.As described in the examples below, depending on the type of acid, the temperature and the hydrolysis time, the surface charge can be modulated.
Ainsi, une hydrolyse par l'acide chlorhydrique conduira à un état de surface quasiment neutre, alors qu'une hydrolyse par l'acide sulfurique introduira des charges sulfates (groupement SO3 -) à la surface des nanocristaux de cellulose.Thus, hydrolysis with hydrochloric acid will lead to a virtually neutral surface state, while hydrolysis by sulfuric acid will introduce sulphate fillers (SO 3 - group ) to the surface of the cellulose nanocrystals.
De tels traitements de type « hydrolyse chimique ménagée » sont par exemple décrits dans le document Elazzouzi-Hafraoui et al. (2008) précité ou dans le document
Par « dissolution/recristallisation », on entend un traitement par un solvant, par exemple acide phosphorique, urée/NaOH, liquides ioniques, etc., suivi d'une recristallisation. Un tel procédé est par exemple décrit dans le document
Avant leur intégration dans la composition, les nanocristaux de cellulose obtenus sont avantageusement soumis à un procédé de post-modification, à l'issue duquel leur densité de charges de surface et/ou leur hydrophobicité / hydrophilicité sont modifiées.Prior to their integration into the composition, the cellulose nanocrystals obtained are advantageously subjected to a post-modification process, at the end of which their surface charge density and / or their hydrophobicity / hydrophilicity are modified.
Cette post-modification vise à optimiser les caractéristiques de surface des nanocristaux de cellulose, notamment en fonction de l'émulsion dans laquelle ils sont introduits, de manière à optimiser sa stabilisation.This post-modification aims to optimize the surface characteristics of the cellulose nanocrystals, in particular according to the emulsion in which they are introduced, in order to optimize its stabilization.
Pour modifier la densité de charges de surface, le procédé de post-modification consiste avantageusement en un procédé d'introduction ou d'hydrolyse de groupements en surface portant lesdites charges de surface.To modify the density of surface charges, the post-modification process advantageously consists of a process for introducing or hydrolyzing surface groups carrying said surface charges.
Dans ce cas, l'opération de post-modification comprend une étape d'introduction ou d'hydrolyse de groupements de surface choisis parmi les groupements sulfonate, carboxylate, phosphate, phosphonate et sulfate.In this case, the post-modification operation comprises a step of introducing or hydrolyzing surface groups chosen from sulphonate, carboxylate, phosphate, phosphonate and sulphate groups.
A titre indicatif, pour l'introduction des groupements de surface respectifs, on peut mettre en oeuvre un procédé tel que décrit dans le document
Encore à titre indicatif et à l'inverse, pour l'hydrolyse de tels groupements de surface, on peut mettre en oeuvre un traitement acide tel que décrit ci-après dans la partie Exemples ou un traitement mécanique de type sonication.Still as an indication and conversely, for the hydrolysis of such surface groups, it is possible to use an acid treatment as described below in the Examples section or a sonication-type mechanical treatment.
Dans ce cadre et selon un premier mode de réalisation, le procédé de fabrication consiste en un procédé d'hydrolyse acide ménagée de la cellulose par l'acide sulfurique, pour obtenir des nanocristaux de cellulose munis de groupements sulfate en surface.In this context and according to a first embodiment, the manufacturing process consists of a process for the acidic hydrolysis of the cellulose with sulfuric acid, to obtain cellulose nanocrystals provided with sulfate groups on the surface.
Et le procédé de post-modification consiste en un procédé d'hydrolyse contrôlée desdits groupements sulfate, à savoir par exemple par un traitement acide (choisi par exemple parmi l'acide chlorhydrique ou l'acide trifluoroacétique) pendant un temps adapté au degré d'hydrolyse recherché.And the post-modification process consists of a controlled hydrolysis process of said sulfate groups, that is, for example by an acid treatment (chosen, for example, from hydrochloric acid or trifluoroacetic acid) for a time adapted to the degree of hydrolysis sought.
Selon un second mode de réalisation, le procédé de fabrication consiste en un procédé d'hydrolyse acide ménagée de la cellulose par l'acide chlorhydrique.According to a second embodiment, the manufacturing process consists of a process for the controlled acid hydrolysis of cellulose with hydrochloric acid.
Et le procédé de post-modification optionnel consiste en un procédé de post-sulfatation desdits nanocristaux de cellulose. Une telle post-sulfatation est avantageusement mise en oeuvre par un traitement acide des nanocristaux à l'acide sulfurique.And the optional post-modification process consists of a post-sulfation process of said cellulose nanocrystals. Such post-sulfation is advantageously carried out by acid treatment of the nanocrystals with sulfuric acid.
Pour modifier l'hydrophobicité, le procédé de post-modification consiste avantageusement en un procédé d'introduction ou d'hydrolyse de groupements présentant un caractère hydrophobe.To modify the hydrophobicity, the post-modification process advantageously consists of a process for introducing or hydrolyzing groups having a hydrophobic character.
Parmi les groupements hydrophobes que l'on peut introduire ou éliminer, on peut citer notamment les groupements alkyle, aryle, phényle, benzyle, acétyle, hydroxybutyle, hydroxypropyle, polycaprolactone (ou PCL).Among the hydrophobic groups that can be introduced or removed include alkyl, aryl, phenyl, benzyl, acetyl, hydroxybutyl, hydroxypropyl, polycaprolactone (or PCL).
A titre indicatif, pour l'introduction et/ou l'hydrolyse des groupements de surface respectifs, on peut se référer aux documents suivants
La présente invention est encore illustrée, sans aucunement être limitée, par les exemples présentés ci-après.The present invention is further illustrated, without being limited, by the examples presented hereinafter.
La
Le procédé d'obtention des nanocristaux de cellulose bactérienne est décrit par exemple dans le document
Des fragments de BCN sont nanofibrilés dans un mélangeur Waring, à pleine vitesse, dans une suspension aqueuse contenant des cubes de glace de sorte à combiner des stress de cisaillement et d'impact.BCN fragments are nanofibrilated in a Waring blender, at full speed, in an aqueous suspension containing ice cubes so as to combine shear and impact stresses.
La pâte ainsi obtenue est égouttée au travers de filtres polyamides, puis suspendue dans une solution d'hydroxyde de sodium 0,5 N sous agitation dans un ballon fermé pendant deux heures à 70°C.The paste thus obtained is drained through polyamide filters and then suspended in a 0.5 N sodium hydroxide solution with stirring in a closed flask for two hours at 70 ° C.
Après élimination des éléments alcalin par le biais de rinçages multiples avec de l'eau ajustée à pH 8, une étape de blanchiment est réalisée avec du chlorite de sorte à obtenir un composé de type hollocellulose, tel que décrit dans Gilkes et al. (
Typiquement, une solution de NaClO2, 17 g/L, est mélangée avec un volume identique de tampon acétate pH 4,5 (27 g de NaOH +75 g d'acide acétique par litre).Typically, a solution of NaClO 2 , 17 g / L, is mixed with an identical volume of acetate buffer pH 4.5 (27 g of NaOH + 75 g of acetic acid per liter).
La cellulose bactérienne blanchie est ensuite suspendue et chauffée sous agitation à 70°C, pendant deux heures avec reflux.The bleached bacterial cellulose is then suspended and heated with stirring at 70 ° C for two hours with reflux.
Ces étapes de traitement alcalin et de blanchiment sont répétées au moins une fois, pour l'obtention d'une pâte blanchie.These alkaline treatment and bleaching steps are repeated at least once, to obtain a bleached pulp.
Cette cellulose bactérienne est ensuite hydrolysée au moyen d'une solution d'acide chlorhydrique (2,5 N, deux heures sous reflux).This bacterial cellulose is then hydrolysed using a hydrochloric acid solution (2.5 N, two hours under reflux).
Les composés acides sont éliminés par les opérations successives jusqu'à neutralité : centrifugation (10000g pendant 5 minutes) et dispersion dans une solution purifiée 18 Mohm.The acidic compounds are removed by the successive operations until neutrality: centrifugation (10000 g for 5 minutes) and dispersion in a purified solution 18 Mohm.
Les nanocristaux de cellulose ainsi obtenus sont conservés à 4°C sous la forme d'une suspension 1%, avec ajout d'une goutte de CHCl3 par 250 mL de suspension.The cellulose nanocrystals thus obtained are stored at 4 ° C. in the form of a 1% suspension, with addition of a drop of CHCl 3 per 250 ml of suspension.
Une suspension aqueuse de nanocristaux de cellulose bactérienne 1,34%, obtenue selon le protocole 1, est mélangée avec une solution de H2SO4 2,2 M (soit un ratio 3/2 v/v) sous agitation vigoureuse à température ambiante.An aqueous suspension of 1.34% bacterial cellulose nanocrystals, obtained according to protocol 1, is mixed with a solution of 2.2 M H 2 SO 4 (ie a 3/2 v / v ratio) with vigorous stirring at room temperature. .
Les nanocristaux sont ensuite déposés par centrifugation (10000 g / 5 min).The nanocrystals are then deposited by centrifugation (10000 g / 5 min).
Le produit obtenu est mélangé avec des billes de verre (diamètre 3 mm), puis centrifugé à nouveau (10000 g / 10 min).The product obtained is mixed with glass beads (diameter 3 mm) and then centrifuged again (10000 g / 10 min).
Les billes de verre recouvertes de nanocristaux sulfatés sont conservées au sec pendant deux heures à 40°C.The glass beads coated with sulfated nanocrystals are kept dry for two hours at 40 ° C.
Les billes sont ensuite séchées au sein d'un dessiccateur, en présence de P2O5 à 50°C pendant 14 heures.The beads are then dried in a desiccator in the presence of P 2 O 5 at 50 ° C for 14 hours.
Les nanocristaux de cellulose sulfatés sont récupérés par lavage des billes à l'eau distillée, et centrifugation successive depuis 10000 tr/min jusqu'à 76000 tr/min pendant 10 à 30 minutes, pour obtenir une suspension colloïdale.The sulphated cellulose nanocrystals are recovered by washing the beads with distilled water, and successive centrifugation from 10,000 rpm to 76,000 rpm for 10 to 30 minutes to obtain a colloidal suspension.
Enfin, le produit collecté est dialysé jusqu'à neutralité, et les électrolytes résiduels sont éliminés sur résine échangeuse d'ions (résine à lit mélangé TMD-8, forme hydrogène et hydroxyde).Finally, the collected product is dialyzed to neutrality, and residual electrolytes are removed on ion exchange resin (mixed bed resin TMD-8, hydrogen and hydroxide form).
La suspension de nanocristaux de cellulose bactérienne à 2,2%, post-sulfatés selon le protocole 2, est chauffée durant trois heures à 100°C dans du HCI 2,5 N, puis lavée par centrifugation à 6000 tr/min pendant 5 minutes à six reprises.The suspension of 2.2% bacterial cellulose nanocrystals, post-sulfated according to protocol 2, is heated for three hours at 100 ° C. in 2.5 N HCl and then washed by centrifugation at 6000 rpm for 5 minutes. six times.
Le produit collecté est ensuite dialysé jusqu'à neutralité, et les électrolytes résiduels sont éliminés sur une résine échangeuse d'ions (résine à lit mélangé TMD-8).The collected product is then dialyzed to neutrality, and residual electrolytes are removed on an ion exchange resin (TMD-8 mixed bed resin).
Le procédé d'obtention des nanocristaux de cellulose de coton est décrit par exemple dans le document Elazzouzi-Hafraoui et al. (2008).The process for obtaining nanocrystals of cotton cellulose is described for example in the document Elazzouzi-Hafraoui et al. (2008).
25 g de papier est humidifié dans 700 mL d'eau déionisée, puis la solution est mélangée jusqu'à obtention d'une mélange homogène. L'excès d'eau est ensuite retiré par filtration.25 g of paper is wetted in 700 ml of deionized water, and the solution is mixed until a homogeneous mixture is obtained. The excess water is then removed by filtration.
Le produit obtenu est suspendu dans 500 mL d'une solution d'acide sulfurique 61 %, maintenu à 72°C sous agitation durant 30 minutes.The product obtained is suspended in 500 ml of a 61% sulfuric acid solution, maintained at 72 ° C. with stirring for 30 minutes.
La suspension est ensuite refroidie, lavée à l'eau ultrapure par centrifugations successives à 8000 tr/min pendant 15 minutes, et dialysée jusqu'à neutralité pendant trois jours avec une phase de réception constituée par de l'eau distillée.The suspension is then cooled, washed with ultrapure water by successive centrifugations at 8000 rpm for 15 minutes, and dialyzed until neutral for three days with a reception phase consisting of distilled water.
Les électrolytes résiduels sont ensuite extraits au moyen d'une résine à lit mélangé (TMD-8, forme hydrogène et hydroxyle) pendant 4 jours.The residual electrolytes are then extracted using a mixed-bed resin (TMD-8, hydrogen and hydroxyl form) for 4 days.
La dispersion finale, constituée de coton sulfaté, est conservée à 4°C.The final dispersion, consisting of sulphated cotton, is stored at 4 ° C.
La désulfatation des nanocristaux de coton sulfatés selon le protocole 4 est réalisée par un traitement acide, au moyen de 5 mL d'une solution d'HCl 5 N ou d'une solution d'acide trifluoroacétique 10 N (TFA), ajoutée à 5 mL d'une suspension de nanocristaux de coton sulfatés à une concentration de 13 g/L.The desulfation of the sulphated cotton nanocrystals according to protocol 4 is carried out by an acid treatment, using 5 ml of a solution of 5 N HCl or a solution of 10 N trifluoroacetic acid (TFA), added to 5 mL of a suspension of sulfated cotton nanocrystals at a concentration of 13 g / L.
Ce traitement acide est mis en oeuvre dans un contenant fermé et chauffé à 98-100°C sous agitation, pendant 1, 2, 5 ou 10 heures.This acid treatment is carried out in a closed container and heated at 98-100 ° C with stirring, for 1, 2, 5 or 10 hours.
De manière alternative, 5 mL d'une solution TFA 10M est ajouté à 5 mL de nanocristaux de coton, avec une incubation durant 10 heures à 80°C sous agitation.Alternatively, 5 mL of a 10M TFA solution is added to 5 mL of cotton nanocrystals, with incubation for 10 hours at 80 ° C with shaking.
Les deux produits obtenus ont été rincés à l'eau par centrifugation (à six reprises, 6000 tr/min pendant 5-7 minutes).The two products obtained were rinsed with water by centrifugation (six times, 6000 rpm for 5-7 minutes).
La titration conductimétrique permet de déterminer le degré de sulfatation des nanocristaux de cellulose.The conductimetric titration makes it possible to determine the degree of sulfation of the cellulose nanocrystals.
Un tel procédé est décrit par exemple dans le document
50 mL d'une suspension aqueuse de nanocristaux de cellulose (0,1 % poids/volume) sont maintenus sous agitation et dégazage pendant 10 minutes, avant titration avec une solution de NaOH 0,01 M.50 ml of an aqueous suspension of cellulose nanocrystals (0.1% w / v) are stirred and degassed for 10 minutes, before titration with a 0.01 M NaOH solution.
La quantité de sulfate greffé est calculée en tenant compte du fait qu'un seul groupement hydroxyle OH peut être substitué par unité glucose, conduisant à un degré de substitution en sulfate (DS) donné par les équations suivantes : 
- Veq est la quantité de NaOH en mL pour atteindre le point d'équivalence,
- CNaoH est la concentration de NaOH exprimée en mol/L,
- Mw est le poids moléculaire moyen d'une unité de glucose,
- m est la masse de cellulose titrée,
- 80 correspond à la différence entre le poids moléculaire d'une unité glucose sulfatée et le poids moléculaire d'une unité glucose non sulfatée.
- V eq is the amount of NaOH in mL to reach the equivalence point,
- C NaoH is the concentration of NaOH expressed in mol / L,
- M w is the average molecular weight of a glucose unit,
- m is the titrated cellulose mass,
- 80 is the difference between the molecular weight of a sulphated glucose unit and the molecular weight of a non-sulphated glucose unit.
La valeur obtenue par ces équations doit être corrigée par la fraction d'unité glucosidique en surface (GSF), pour obtenir le degré de substitution en surface désigné « DSs ».The value obtained by these equations must be corrected by the surface glycosidic unit (GSF) fraction, to obtain the degree of surface substitution designated "DSs".
Selon la structure des chaînes cellulosiques, seuls les groupes OH primaires (en C6) peuvent être estérifiés, et seulement 50% de ces groupes OH sont accessibles à la surface en raison de la conformation en alternance. Le DSs maximal est ainsi de 0,5.Depending on the structure of the cellulosic chains, only the primary (C6) OH groups can be esterified, and only 50% of these OH groups are accessible at the surface due to the alternating conformation. The maximum DSs is thus 0.5.
Etant donné que les échantillons varient en morphologie et pour une application générale à tous les différentes particules cellulosiques, une équation générale a été définie afin de déterminer la valeur de fraction de glucose en surface (GSF) tenant compte du ratio de la section transversale (k) quelle que soit la longueur des particules.Since the samples vary in morphology and for general application to all the different cellulosic particles, a general equation has been defined in order to determine the surface glucose fraction (GSF) value taking into account the ratio of the cross section (k). ) regardless of the length of the particles.
Ainsi, pour une largeur donnée (Wxl) et un ratio d'aspect (k), on a : 
20 µL d'une suspension aqueuse de nanocristaux de cellulose (0,1 % poids/volume) sont déposés sur une grille carbonée pour microscopie électronique ; l'excès de solvant absorbé, l'échantillon est marqué par ajout d'acétate d'uranyle (2% dans l'eau).20 μl of an aqueous suspension of cellulose nanocrystals (0.1% w / v) are deposited on a carbon grid for electron microscopy; the excess of absorbed solvent, the sample is marked by addition of uranyl acetate (2% in water).
Cette grille pour microscopie électronique est ensuite séchée dans une étuve à 40°C.This grid for electron microscopy is then dried in an oven at 40 ° C.
Les grilles ont ensuite été observées avec un microscope électronique en transmission de marque JEOL (80kV).The grids were then observed with a transmission electron microscope JEOL brand (80kV).
Une première émulsion de Pickering huile dans l'eau est préparée en utilisant une phase aqueuse contenant une concentration connue de nanocristaux de cellulose.A first oil-in-water Pickering emulsion is prepared using an aqueous phase containing a known concentration of cellulose nanocrystals.
Les autres émulsions ont été préparées en utilisant un ratio 30/70 huile/eau à partir d'une phase aqueuse contenant des nanoparticules à une concentration de 0,5 % en poids, par rapport au poids de l'émulsion (sans dilution supplémentaire).The other emulsions were prepared using a 30/70 oil / water ratio from an aqueous phase containing nanoparticles at a concentration of 0.5% by weight, based on the weight of the emulsion (without further dilution) .
Dans un tube Eppendorf, 0.3 mL d'hexadécane sont ajoutés à 0,7 mL de la suspension aqueuse ; pendant 30 secondes, le mélange est soumis à un traitement alternant 2 secondes de traitement ultrason et 5 secondes de repos.In an Eppendorf tube, 0.3 mL of hexadecane is added to 0.7 mL of the aqueous suspension; for 30 seconds, the mixture is subjected to a treatment alternating 2 seconds of ultrasound treatment and 5 seconds of rest.
Les émulsions obtenues selon le protocole 8 sont centrifugées pendant 30 secondes à 10000 g. Etant donné la différence de densité entre l'hexadécane et l'eau, un crémage est observé. Le volume d'émulsion est évalué avant et après centrifugation.The emulsions obtained according to protocol 8 are centrifuged for 30 seconds at 10,000 g. Given the difference in density between hexadecane and water, creaming is observed. The emulsion volume is evaluated before and after centrifugation.
Environ 15 µL de la solution de Pickering est incorporé dans 1 mL d'eau distillée. Le produit est mélangé par vortex, puis une goutte est déposée sur une lamelle pour observation au microscope.About 15 μL of the Pickering solution is incorporated in 1 mL of distilled water. The product is mixed by vortex, then a drop is deposited on a coverslip for observation under a microscope.
Le diamètre des gouttelettes est mesuré à partir des images obtenues, par analyse d'images en utilisant un programme « imageJ »,.The droplet diameter is measured from the images obtained by image analysis using an "imageJ" program.
Ces résultats ont par ailleurs été comparés à la distribution des tailles de gouttes déterminée par un dispositif Malvern MasterSizer employant un dispositif à diffraction de la lumière avec analyse par équation Fraunhofer. Le risque d'agrégation est dans ce cas limité par l'ajout de SDS (Sodium Dodécyl Sulfate) juste avant la mesure.These results were further compared to the droplet size distribution determined by a Malvern MasterSizer device employing a Fraunhofer equation analysis light scattering device. In this case, the risk of aggregation is limited by the addition of SDS (Sodium Dodecyl Sulfate) just before the measurement.
Pour préparer l'échantillon d'émulsion pour son observation par microscopie électronique à balayage (MEB), 280-380 mg d'un mélange styrène/initiateur (ratio st : V-65 120:1 poids/poids) sont mélangés avec 1,0 à 1,5 mL de solution à 0,5% d'un solution échantillon d'eau, soumis aux ultrasons pendant 1-2 min et dégazés avec de l'azote pendant 10 minutes.To prepare the emulsion sample for observation by scanning electron microscopy (SEM), 280-380 mg of a styrene / initiator mixture (ratio st: V-65 120: 1 w / w) are mixed with 1, 0 to 1.5 mL of 0.5% solution of a water sample solution, sonicated for 1-2 min and degassed with nitrogen for 10 minutes.
L'émulsion a été obtenue par ultrasons pendant 30 secondes (impulsion de 3 secondes, séparées de 5 secondes).The emulsion was ultrasonically obtained for 30 seconds (pulse of 3 seconds, separated by 5 seconds).
Puis 500µL d'eau sont ajoutés dans le système, traité ensuite par vortex.Then 500μL of water is added to the system, then treated by vortexing.
Ce système est dégazé avec de l'azote pendant 10 minutes, et la polymérisation a eu lieu à 63°C sans agitation pendant 24h.This system is degassed with nitrogen for 10 minutes, and the polymerization took place at 63 ° C without stirring for 24 hours.
La préparation résultante est soumise à une étape de métallisation selon les techniques conventionnelles de microscopie électronique à balayage, avant observation.The resulting preparation is subjected to a metallization step according to conventional techniques of scanning electron microscopy, before observation.
Pour son observation par microscopie électronique à balayage, l'échantillon d'émulsion peut encore être préparé avec un autre initiateur, à savoir l'AIBN (azobisisobutyronitrile), selon le protocole suivant :
- dégazage et agitation de 17,5 mL de suspension de nanocristaux à 3 g/
L 50 mM,pendant 10 min sous azote, - ajout de 7,5 mL de styrène et de 69,8 mg d'AIBN,
- émulsification aux ultrasons pendant 1min,
- dégazage pendant 10min, et
- polymérisation sous agitation à 70°C, entre 1h et 24h.
- degassing and stirring 17.5 mL suspension of nanocrystals at 3 g /
L 50 mM, for 10 min under nitrogen, - addition of 7.5 mL of styrene and 69.8 mg of AIBN,
- ultrasonic emulsification for 1min,
- degassing for 10min, and
- polymerization with stirring at 70 ° C, between 1h and 24h.
5 mL d'une suspension de nanocristaux de cellulose bactérienne 1,34% sont mélangés avec 40 mL d'une solution d'acide acétique 100%.5 ml of a suspension of 1.34% bacterial cellulose nanocrystals are mixed with 40 ml of a solution of 100% acetic acid.
L'eau est graduellement remplacée par l'acide acétique par distillation sur un évaporateur rotatif (la température du bain d'eau est inférieure à 40°C), puis centrifugée à cinq reprise (5 minutes à 10000 g).The water is gradually replaced by acetic acid by distillation on a rotary evaporator (the temperature of the water bath is below 40 ° C), then centrifuged five times (5 minutes at 10000 g).
40 mL de l'échantillon d'acide acétique sont divisés en deux parties.40 mL of the acetic acid sample is divided into two parts.
Les deux parties sont mélangées et chauffées à 40°C pendant 5 minutes et pendant 1 minute avec 6 µL d'un catalyseur à 5 %.The two parts are mixed and heated at 40 ° C. for 5 minutes and for 1 minute with 6 μl of a 5% catalyst.
Ensuite, 2,5 mL d'un mélange constitué d'anhydride acétique 98 % et d'acide acétique 100 % (dans un ratio 1:1 volume/volume) sont ajoutés.Then, 2.5 mL of a mixture consisting of 98% acetic anhydride and 100% acetic acid (in a 1: 1 v / v ratio) are added.
La solution échantillon est observée sous une lumière polarisée de manière à détecter la présence de cristaux liquides.The sample solution is observed under polarized light so as to detect the presence of liquid crystals.
La réaction est stoppée par l'ajout d'eau (ratio 1:1 v/v), soit après une minute pour une partie (B1), soit après trois minutes pour l'autre partie (B2).The reaction is stopped by the addition of water (ratio 1: 1 v / v), either after one minute for one part (B1), or after three minutes for the other part (B2).
Une ultracentrifugation finale (10000 g pendant 10-30 minutes) de toutes les solutions obtenues permet de collecter et de rincer le produit.Final ultracentrifugation (10000 g for 10-30 minutes) of all the solutions obtained makes it possible to collect and rinse the product.
Le produit obtenu est mélangé avec une résine à lit mélangé pendant trois heures, puis ensuite filtré.The resulting product is mixed with a mixed bed resin for three hours and then filtered.
10 mL d'une suspension à 2,4% en masse de nanoparticules de coton désulfatées (voir protocole 5 - les nanoparticules ont été désulfatées par HCI 2,5 N pendant 3 h) sont mélangés avec 90 mL d'acide acétique 100%.10 ml of a 2.4% suspension by weight of desulfated cotton nanoparticles (see protocol 5 - the nanoparticles were desulfated by 2.5 N HCl for 3 h) are mixed with 90 ml of 100% acetic acid.
L'eau est progressivement remplacée par l'acide acétique par distillation sur un évaporateur rotatif (la température du bain d'eau était inférieure à 40°C), puis centrifugation 5 fois 7min à 10000g.The water is gradually replaced by acetic acid by distillation on a rotary evaporator (the temperature of the water bath was below 40 ° C), and then centrifugation 5 times 7min at 10000g.
80 mL de volume de l'échantillon dans l'acide acétique sont divisés en 2 fractions.80 mL of sample volume in acetic acid are divided into 2 fractions.
Les deux fractions ont été chauffées à 60°C avec 190 µL de catalyseur, à savoir une solution d'acide sulfurique à 5% en masse dans l'acide acétique, et agité.The two fractions were heated at 60 ° C with 190 μl of catalyst, i.e. 5% by weight sulfuric acid solution in acetic acid, and stirred.
Après 5 minutes, 5 mL d'un mélange constitué d'anhydride acétique à 98% et d'acide acétique à 100%, dans un ratio 1:1 v / v, sont ajoutés ; et la solution de l'échantillon a été mis sous observation en lumière polarisée pour observer le comportement des cristaux liquides de l'échantillon.After 5 minutes, 5 ml of a mixture consisting of 98% acetic anhydride and 100% acetic acid, in a ratio 1: 1 v / v, are added; and the solution of the sample was observed under polarized light to observe the behavior of the liquid crystals of the sample.
Lorsque la transformation en cristaux liquides est observée, la réaction est arrêtée par refroidissement dans un bain d'eau glacé ; 10 mL d'acide acétique 80% est en plus versé dans le ballon puis de l'eau, soit la moitié du volume de solution de l'échantillon.When the transformation into liquid crystals is observed, the reaction is stopped by cooling in an ice-water bath; 10 ml of 80% acetic acid is additionally poured into the flask and then water, which is half the volume of solution in the sample.
La réaction est arrêtée après 1,5 min pour la première fraction, et après 0,5 min pour la seconde.The reaction is stopped after 1.5 min for the first fraction, and after 0.5 min for the second.
Enfin, une ultracentrifugation (65000 tr/mn pendant 15-30min) de la solution de second échantillon obtenu est réalisée afin de recueillir et de rincer les produits ; les électrolytes résiduels sont enlevés par résine échangeuse d'ions pendant 3 h avant la filtration.Finally, an ultracentrifugation (65,000 rpm for 15-30 min) of the second sample solution obtained is carried out in order to collect and rinse the products; residual electrolytes are removed by ion exchange resin for 3 hours before filtration.
Une partie de l'échantillon (c-wh 3) est chauffée à 40°C sous agitation, pendant 5 minutes, puis après 1min avec 190µL de catalyseur à 5% (voir ci-dessus).Part of the sample (c-wh 3) is heated at 40 ° C. with stirring, for 5 minutes, then after 1 min with 190 μl of 5% catalyst (see above).
Puis 5 mL d'un mélange constitué d'anhydride acétique à 98% et d'acide acétique à 100% (ratio 1:1 v / v) sont ajoutés, et la solution échantillon est observée sous lumière polarisée pour vérifier le comportement des cristaux liquides de l'échantillon.Then 5 mL of a mixture consisting of 98% acetic anhydride and 100% acetic acid (ratio 1: 1 v / v) are added, and the sample solution is observed under polarized light to check the behavior of the crystals. sample liquids.
La réaction est arrêtée après 1 min par l'ajout d'eau dans le rapport 1:1 v / v.The reaction is stopped after 1 min by the addition of water in the ratio 1: 1 v / v.
L'autre partie (c-wh 4) est chauffée à 40°C sous agitation pendant 5 minutes, puis sont ajoutés 5 mL d'un mélange constitué d'anhydride acétique à 98% et d'acide acétique à 100% dans un rapport 1:1 v / v.The other part (c-wh 4) is heated at 40 ° C. with stirring for 5 minutes, and then 5 ml of a mixture consisting of 98% acetic anhydride and 100% acetic acid in a ratio are added. 1: 1 v / v.
Puis 6µL d'un catalyseur à 5% (voir ci-dessus) sont ajoutés dans le mélange ; la réaction est arrêtée en 1 min en rapportant de l'eau dans un rapport 1:1 v / v.Then 6μL of a 5% catalyst (see above) is added to the mixture; the reaction is stopped in 1 min by bringing water in a 1: 1 v / v ratio.
Enfin, toutes les solutions sont soumises à une ultracentrifugation (65000 tr/mn pendant 15-30min) afin de recueillir et de rincer les produits ; les électrolytes résiduels sont enlevés par résine échangeuse d'ions pendant 3 h avant filtration.Finally, all solutions are subjected to ultracentrifugation (65,000 rpm for 15-30min) to collect and rinse the products; the residual electrolytes are removed by ion exchange resin for 3 hours before filtration.
10 mL d'une solution à 2,4% en masse de whiskers de coton désulfatés (c-wh est désulfaté par HCI 2,5 N pendant 3 h) sont mélangés avec 90 mL d'acide acétique à 100% ; l'eau est éliminée au moyen d'un évaporateur rotatif (la température du bain d'eau obtenue est inférieure à 40°C).
- a) 4 mL d'anhydride acétique à 98% sont ajoutés à 40 mL de la solution obtenue après 1 min sous agitation, puis environ 90 mL d'eau sont ajouté (1AA-d-c-WH).
- b) 12 mL d'anhydride acétique à 98% sont ajoutés dans 40 mL de solution obtenue après 15 min sous agitation, puis environ 80 mL d'eau sont ajoutés (3AA-d-c-WH).
- a) 4 ml of 98% acetic anhydride are added to 40 ml of the solution obtained after stirring for 1 min, then about 90 ml of water are added (1AA-dc-WH).
- b) 12 ml of 98% acetic anhydride are added in 40 ml of solution obtained after stirring for 15 min, then about 80 ml of water are added (3AA-dc-WH).
Les deux échantillons sont lavés à l'eau par centrifugation, et conservés avec un lit de résine pendant 3h, puis filtrées.The two samples are washed with water by centrifugation, and kept with a bed of resin for 3 hours, then filtered.
5 mL d'une solution à 2,4% en masse de whiskers de coton désulfatés (c-wh est désulfaté par HCI 2,5 N pendant 3 h) sont mélangés avec 0,5 mL d'acide anhydride à 98%, la réaction étant maintenue pendant 10min sous agitation ; la même procédure est répétée 9 fois.5 ml of a 2.4% by weight solution of desulfated cotton whiskers (c-wh is desulfated by 2.5 N HCl for 3 h) are mixed with 0.5 ml of 98% anhydride acid, the reaction being maintained for 10 min with stirring; the same procedure is repeated 9 times.
Le mélange est ensuite divisé en deux fractions.
- a) une fraction est lavée avec de l'eau par centrifugation et conservée avec un lit de résine pendant 3 h, puis filtré (fraction STW1)
- b) l'autre fraction est conservée en présence de l'acide anhydride à 4°C une nuit, rincée à l'eau par centrifugation et conservée avec un lit de résine pendant 3 h, puis filtré (fraction STW2)
- a) a fraction is washed with water by centrifugation and kept with a bed of resin for 3 h, then filtered (fraction STW1)
- b) the other fraction is kept in the presence of the anhydride acid at 4 ° C overnight, rinsed with water by centrifugation and kept with a bed of resin for 3 h, then filtered (STW2 fraction)
Le greffage en surface de poly-e-caprolactone est réalisé sur BCN et whiskers de coton.The surface grafting of poly-ε-caprolactone is carried out on BCN and cotton whiskers.
50mg de whiskers séchés sont mélangés avec 860mg de e-caprolactone pendant 48h.50mg of dried whiskers are mixed with 860mg of e-caprolactone for 48h.
800mg de poly-e-caprolactone sont ensuite ajoutés, et la dispersion est soumise à un traitement 5x10sec.800 mg of poly-ε-caprolactone are then added, and the dispersion is subjected to 5 × 10 sec treatment.
1,5µL d'alcool benzylique sont ajoutés en tant que co-initiateur, puis dégazé à l'azote pendant 30 min.1.5 μl of benzyl alcohol are added as a co-initiator and then degassed with nitrogen for 30 min.
La solution est chauffée à 95°C ; 27µL de Sn(Oct)2 est ajouté sous atmosphère azotée.The solution is heated to 95 ° C; 27 μl of Sn (Oct) 2 is added under a nitrogen atmosphere.
La polymérisation est poursuivie pendant 18h, avant redispersion du produit dans 2 mL de THF, filtré et rincé avec du méthanol.The polymerization is continued for 18 h, before redispersion of the product in 2 mL of THF, filtered and rinsed with methanol.
Les nanocristaux de cellulose bactérienne sont obtenues selon le protocole 1, et consistent en des particules neutres.The nanocrystals of bacterial cellulose are obtained according to protocol 1, and consist of neutral particles.
Comme montré ci-dessous, ces nanocristaux présentent d'excellentes propriétés pour former des émulsions de Pickering particulièrement stables.As shown below, these nanocrystals have excellent properties for forming particularly stable Pickering emulsions.
De telles émulsions ont été réalisées selon le protocole 8, pour différents ratios hexadécane / phase aqueuse, à savoir depuis un ratio 10:90 jusqu'à un ratio 50:50.Such emulsions were made according to protocol 8, for different hexadecane / aqueous phase ratios, namely from a 10:90 ratio to a 50:50 ratio.
Ainsi, la concentration en particules dans les émulsions varie avec la fraction volumique de l'eau dans lesdites émulsions.Thus, the particle concentration in the emulsions varies with the volume fraction of the water in said emulsions.
L'analyse par microscopie optique selon le protocole 9 donne les résultats précisés dans le tableau 1 ci-dessous.
Les mesures de nombre de gouttes, d'aire moyenne, de diamètre moyen en nombre (Dn moyen), de diamètre moyen en poids (Dw moyen), de polydispersité (Dw moyen / Dn moyen) et de pourcentage d'agrégats, ont été mesurés comme décrit par
Pour ces différents ratios, approximativement le même diamètre moyen est mesuré par analyse d'image, à savoir 4±2 µm avec une polydispersité de 1,13 ±0.2.For these different ratios, approximately the same average diameter is measured by image analysis, namely 4 ± 2 μm with a polydispersity of 1.13 ± 0.2.
La principale différence concerne le taux d'agrégation qui diminue avec la diminution de la quantité de particules par mL de phase hydrophobe.The main difference concerns the rate of aggregation which decreases with the decrease in the amount of particles per mL of hydrophobic phase.
Selon ces résultats et afin de limiter les phénomènes d'agrégations, un ratio de 30:70 est choisi pour les expériences suivantes.According to these results and in order to limit the phenomena of aggregations, a ratio of 30:70 is chosen for the following experiments.
La stabilité des échantillons, conservés dans des conditions différentes (temps, température), est évaluée selon le protocole 9.The stability of the samples, preserved under different conditions (time, temperature), is evaluated according to protocol 9.
Aucune variation de la taille des gouttelettes n'a été observée, même après le maintien des échantillons pendant un mois à 4°C ou 40°C, ou jusqu'à 3 heures à 80°C.No variation in droplet size was observed, even after holding the samples for one month at 4 ° C or 40 ° C, or up to 3 hours at 80 ° C.
Les nanocristaux de cellulose bactérienne obtenus selon les protocoles 1 à 5, sont caractérisés par microscopie électronique en transmission conformément au protocole 7. Les caractéristiques de surfaces de nanocristaux et les caractéristiques de l'émulsion sont déterminées selon les protocoles 6 et 9.
Les résultats obtenus sont récapitulés dans le tableau 2 suivant.
The results obtained are summarized in the following Table 2.
On précise que pour le Tableau 2, la densité de charge peut être exprimée indifféremment en e.nm-2 ou en sulfate.nm-2, du fait que l'ion sulfate porte une charge unique.It is specified that for Table 2, the charge density can be expressed indifferently in e.nm -2 or in sulfate.nm-2, because the sulfate ion carries a single charge.
Les analyses en microscopie électronique montrent que les particules ont toutes une forme allongée.The electron microscopic analyzes show that the particles all have an elongated shape.
Pour tous les nanocristaux de cellulose, l'hydrolyse par l'acide sulfurique a tendance à diminuer la longueur. Par exemple, la BCN est diminuée en passant de 919 nm à 644 nm, sans variation notable de largeur après l'étape de sulfatation.For all cellulose nanocrystals, sulfuric acid hydrolysis tends to decrease the length. For example, the BCN is decreased from 919 nm to 644 nm without significant variation in width after the sulfation step.
En revanche, l'hydrolyse par l'acide chlorhydrique a tendance à peler la surface des nanocristaux de cellulose et ainsi à réduire ou même éliminer les groupes sulfate, et donc réduire ou éliminer les charges correspondantes.On the other hand, the hydrolysis with hydrochloric acid tends to peel the surface of the cellulose nanocrystals and thus reduce or even eliminate the sulfate groups, and thus reduce or eliminate the corresponding charges.
L'émulsion correspondante est très stable (au moins une année), et résiste à la congélation et au chauffage (2 heures à 80°C).The corresponding emulsion is very stable (at least one year), and resists freezing and heating (2 hours at 80 ° C).
On a préparé des émulsions à partir de nanocristaux de cellulose de coton comme décrit dans le Protocole 8Emulsions were prepared from cotton cellulose nanocrystals as described in Protocol 8
Pour la préparation d'émulsions, on a utilisé un milieu aqueux ayant des valeurs croissantes de force ionique.For the preparation of emulsions, an aqueous medium having increasing values of ionic strength has been used.
Plus précisément, on a utilisé des milieux aqueux liquides ayant des valeurs croissantes de concentration finale en NaCl, comme indiqué dans le Tableau 3 ci-dessous.
Les résultats sont présentés simultanément dans le Tableau 3 et la
Les résultats présentés dans le tableau 3 montrent l'évolution de l'épaisseur de l'émulsion obtenue après crémage (centrifugation) ; il s'agit d'une valeur relative en mm, d'un pourcentage volumique émulsionné et des valeurs de potentiel zeta qui illustre le niveau d'écrantage des charges de surface par le NaCl ajouté.The results presented in Table 3 show the evolution of the thickness of the emulsion obtained after creaming (centrifugation); it is a relative value in mm, an emulsified volume percentage and zeta potential values which illustrates the level of screening of the surface charges by the added NaCl.
Les résultats présentés sur la
Claims (15)
- A composition in the form of an emulsion comprising a hydrophobic phase dispersed in an aqueous phase, which composition contains emulsifying particles capable of stabilizing said emulsion, wherein at least some of said particles do consist of cellulose nanocrystals having an elongated shape which satisfy the following features: a length ranging from 25 nm to 1 µm, and a width ranging from 5 to 30 nm.
- A composition according to claim 1, wherein the cellulose nanocrystals satisfy the following features: a length ranging from 100 nm to 1 µm, and a width ranging from 5 to 20 nm.
- A composition according to claim 1 or 2, wherein the cellulose nanocrystals have a length to width ratio higher than 1 and lower than 100, and preferably ranging from 10 to 55.
- A composition according to any of the claims 1 to 3, wherein the cellulose nanocrystals have a surface charge density of maxi. 0.5 e.nm-2, e standing for elementary electric charge.
- A composition according to claim 4, wherein the cellulose nanocrystals comprise a charged surface, with a surface charge density ranging from 0.01 e.nm-2 to 0.31 e.nm-2.
- A composition according to claim 5, wherein the cellulose nanocrystals comprise surface negative charges,
wherein the cellulose nanocrystals have preferably surface charge-carrying anionic groups on the surface thereof,
wherein the anionic groups of the cellulose nanocrystals are preferably chosen from sulfonate, carboxylate, phosphate, phosphonate and sulfate groups. - A composition according to claim 4, wherein the cellulose nanocrystals have a neutral surface, the surface charge density being lower than or equal to 0.01 e.nm-2.
- A composition according to any one of claims 1 to 7, wherein said composition has an ionic force lower than an ionic force corresponding to 10 mM NaCl, and wherein the cellulose nanocrystals have a surface charge density of maxi. 0.03 e.nm-2.
- A composition according to any one of claims 1 to 8, wherein the cellulose nanocrystals have hydrophobic groups on the surface thereof,
wherein the hydrophobic groups of the cellulose nanocrystals do consist preferably of acetyl groups. - A composition according to any one of claims 1 to 9, wherein- said composition comprises from 0.035% to 2% by weight, preferably from 0.05% to 1% by weight, of cellulose nanocrystals relative to the total weight of said composition, and/or,- the hydrophobic phase represents from 5% to 45% by weight relative to the total weight of said composition, and/or- the hydrophobic phase is selected from vegetable oils, animal oils, mineral oils, synthetic oils, hydrophobic organic solvents and hydrophobic liquid polymers, and/or- the composition is selected from food compositions, cosmetic compositions, pharmaceutical compositions and phytosanitary compositions.
- Use of cellulose nanocrystals such as defined in any one of claims 1 to 9, to stabilize an emulsion comprising a hydrophobic phase dispersed in an aqueous phase.
- A method for preparing a composition in the form of an emulsion according to any one of claims 1 to 10, which comprises the following steps of:(a) providing cellulose nanocrystals such as defined in any one of claims 1 to 9, thereafter(b) incorporating said cellulose nanocrystals to the aqueous phase of said composition, so as to stabilize said emulsion.
- A method according to claim 12, wherein the cellulose nanocrystals provided in step (a) are obtained through a production method from a cellulose, said production method being selected from the following methods: mechanical fractionation, adjusted chemical hydrolysis, and dissolution/recrystallization,
wherein the method for making cellulose nanocrystals is preferably followed with a method of post-modification of said cellulose nanocrystals, at the end of which their surface charge density and/or their hydrophobicity are modified,
wherein the post-modification method does consist preferably of a method for introducing or hydrolyzing surface charge-carrying groups,
wherein the post-modification process comprises preferably a step of introducing or hydrolyzing surface groups chosen from sulfonate, carboxylate, phosphate, phosphonate and sulfate groups. - A method according to claim 13, wherein:- the production method does consist of a sulfuric acid-mediated adjusted acid hydrolysis method for cellulose, to obtain cellulose nanocrystals provided with sulfate groups on their surface, and wherein the optional post-modification process does consist of a controlled hydrolysis for said sulfate groups, or- the production method does consist of a hydrochloric acid-mediated adjusted acid hydrolysis method for cellulose, and wherein the optional post-modification method does consist of a post-sulfation process of said cellulose nanocrystals.
- A method according to any one of claims 13 or 14, wherein the cellulose is selected amongst at least one from the various following origins thereof: plants, animals, bacteria, algae or from those regenerated from a transformed cellulose available on the market.
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| PCT/FR2011/051717 WO2012017160A1 (en) | 2010-07-19 | 2011-07-18 | Composition in the form of an emulsion, comprising a hydrophobic phase dispersed in an aqueous phase |
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| FI127526B (en) | 2012-11-03 | 2018-08-15 | Upm Kymmene Corp | Method for producing nanofibrillar cellulose |
| US10010490B2 (en) * | 2012-12-04 | 2018-07-03 | Nissan Chemical Industries, Ltd. | Cosmetic composition comprising cellulose fibers with small fiber diameter and comparatively small aspect ratio |
| US20140322428A1 (en) | 2013-03-15 | 2014-10-30 | Leading Edge Innovations, LLC | Compositions having an oil-in-water dispersion of submicron particles to enhance foods and beverages |
| BR112015023340B1 (en) | 2013-03-15 | 2020-05-05 | Leading Edge Innovations Llc | substantially surfactant-free composition, method for applying aesthetic modifying agents and method for imparting a tactile, olfactory or visual property to the skin, hair or mucosal surface |
| JP6216574B2 (en) * | 2013-08-29 | 2017-10-18 | 王子ホールディングス株式会社 | Emulsifier containing fine cellulose fiber, emulsified composition and emulsification method |
| US20170000903A1 (en) * | 2013-11-28 | 2017-01-05 | University Of Saskatchewan | Crystalline cellulose gel-based cryptands, surface active agents, emulsions and vesicles |
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| FR2794466B1 (en) * | 1999-06-02 | 2001-06-29 | Oreal | COMPOSITION IN THE FORM OF AN OIL-IN-WATER EMULSION CONTAINING CELLULOSE FIBRILLES AND ITS IN PARTICULAR COSMETIC USES |
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| FR2903595B1 (en) * | 2006-07-11 | 2008-08-22 | Rhodia Recherches & Tech | COSMETIC COMPOSITIONS COMPRISING A THERMOPLASTIC MATERIAL POWDER |
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| US7994111B2 (en) * | 2008-02-15 | 2011-08-09 | The Procter & Gamble Company | Liquid detergent composition comprising an external structuring system comprising a bacterial cellulose network |
| JP5586833B2 (en) | 2008-02-21 | 2014-09-10 | 花王株式会社 | Resin composition |
| JP2010116477A (en) * | 2008-11-13 | 2010-05-27 | Sumitomo Bakelite Co Ltd | Composite composition |
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